hydrogen-04-00049

Review
The Effect of Electrolytes on the Kinetics of the Hydrogen

Evolution Reaction
Goitom K. Gebremariam 1,2 , Aleksandar Z. Jovanović 1 and Igor A. Pašti 1, *
1 Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12–16, 11158 Belgrade, Serbia;
nebyat1997@gmail.com (G.K.G.); a.jovanovic@ffh.bg.ac.rs (A.Z.J.)
2 Department of Chemistry, Mai Nefhi College of Science, National Higher Education and Research Institute,
Asmara 12676, Eritrea
* Correspondence: igor@ffh.bg.ac.rs; Tel.: +381-11-3336-625
Abstract: Amid global energy challenges, the hydrogen evolution reaction (HER) is gaining traction
for green hydrogen production. While catalyst research is ongoing, recognizing electrolyte effects
remains crucial for sustainable hydrogen production via renewable-powered water electrolysis. This
review delves into the intricate effects of electrolytes on the kinetics of the HER. It examines key fac-
tors including the pH, cations, anions, impurities, and electrolyte concentration. This review discusses
the notion that the electrolyte pH alters catalyst–electrolyte interactions and proton concentrations,
thereby influencing factors such as the hydrogen binding energy, water adsorption, and overall reac-
tion kinetics. Moreover, this review provides a briefing on the notion that electrolyte cations such as
Li+ can impact the HER positively or negatively, offering opportunities for improvement based on the
metal substrate. Interestingly, there is a potential that the HER can be tuned using Li+ ions to modify
the M–H bond energy, demonstrating a flexibility beyond the pH levels and counter-ions. The varied
adsorption energies of metal cations on metal electrodes are also found to influence the HER kinetics.
The effects of electrolyte anions and impurities are also discussed, emphasizing both the positive
and negative impacts on HER kinetics. Moreover, it is pointed out that the electrolyte-engineering
approach enhances the HER kinetics without permanent catalyst surface modifications. This review
underscores the importance of the electrolyte composition, highlighting both the challenges and
potential solutions in advancing HER research for sustainable energy production.
Keywords: hydrogen evolution reaction; kinetics; electrolyte; electrolyte ions; electrolyte impurities;
electrolyte engineering
Citation: Gebremariam, G.K.;
Jovanović, A.Z.; Pašti, I.A. The Effect
of Electrolytes on the Kinetics of the
Hydrogen Evolution Reaction.
1. Introduction
Hydrogen 2023, 4, 776–806. https://
doi.org/10.3390/hydrogen4040049
1.1. Background Information on the Hydrogen Evolution Reaction
In the 21st century, pressing issues include the depletion of non-renewable energy
Received: 13 September 2023
sources, the environmental harm from fossil fuels, and the escalating global energy demand.
Revised: 7 October 2023
With fossil fuels being responsible for 84% of energy consumption, their use leads to severe
Accepted: 9 October 2023
Published: 13 October 2023
environmental issues. Researchers are investigating renewable energy sources such as
solar, wind, and biomass sources to address the environmental problems and growing
energy demands. However, these sources are intermittent, necessitating the use of efficient
energy transformation and storage technologies. Efficient energy storage methods are
Copyright: © 2023 by the authors. vital for a reliable energy supply, especially with the rise of renewables, with an emphasis
Licensee MDPI, Basel, Switzerland. on electrochemical energy storage systems like batteries. However, these systems lead to
This article is an open access article environmental issues due to their material toxicity and energy-intensive manufacturing
distributed under the terms and processes. Thus, hydrogen, renowned for its high energy density and emission-free com-
conditions of the Creative Commons bustion by-product, is a widely explored energy carrier, while water splitting utilizing
Attribution (CC BY) license (https://
surplus electricity from renewables holds promise for clean hydrogen production [1]. This
creativecommons.org/licenses/by/
method ensures a high energy conversion efficiency [2–4], promoting its use in fuel cells
4.0/).
Hydrogen 2023, 4, 776–806. https://doi.org/10.3390/hydrogen4040049 https://www.mdpi.com/journal/hydrogen

Hydrogen 2023, 4 777
or combustion for a greener future [5–8]. As summarized in [9], global hydrogen demand
is expected to surpass 500 Mt by 2050, generating around USD 3 trillion in revenue [10].
Currently, 95% of hydrogen comes from so-called grey hydrogen, emitting 10 kg of CO2 per
1 kg of hydrogen produced. Green hydrogen from water electrolysis by renewable sources
is eco-friendly but costs about four to five times more than grey hydrogen due to electricity
expenses [11]. Thus, improving the efficiency of water electrolysis technologies is crucial to
achieving lower production costs.
Solar water splitting is anticipated to serve as the cornerstone of a sustainable hydrogen-
based energy economy. This process offers a carbon-neutral means of producing hydrogen
gas, utilizing abundant renewable resources—water and sunlight. Ref. [12] provides a
comprehensive review of the current state of direct water splitting in photo-electrochemical
cells (PECs). The study includes a case study using a simple solar cell with efficient water-
splitting electrodes and a detailed mechanism analysis. Additionally, the review offers
an in-depth analysis of the energy balance and efficiency in solar hydrogen production.
A demonstration employing a ~0.7%-efficient n-Si/Ni Schottky solar cell connected to a
water electrolysis cell was observed to attain an impressive 52% solar hydrogen produc-
tion efficiency. Emphasizing the separation of solar harvesting and electrolysis processes
prevents photo-electrode corrosion and optimizes electrodes for the HER and OER; this
approach attains ~10% efficiency when paired with conventional 18%-efficient Si-solar cells
commonly used on household roofs. The review also outlined a strategy to surpass 15%
efficiency for a single junction cell.
Water electrolysis involves two simultaneous electrochemical reactions, the hydrogen
evolution reaction (HER) at the cathode and the oxygen evolution reaction (OER) at the an-
ode, occurring in a typical cell with an anode, cathode, power source, and electrolyte [2,13].
The theoretical minimum energy for water splitting is 1.23 V at ambient temperature [13].
However, due to the polarization overpotential of the cathode and anode and the internal
resistance of the electrolyte, additional energy is required, known as the cell overpoten-
tial [14,15]. Efficient electrocatalysts are crucial for both the HER and OER processes to
improve the energy conversion efficiency and minimize overpotential. In spite of the fact
that the HER is vital for transforming electrical energy into chemical energy in the form
of an H2 molecule, the OER also plays a significant part in the overall efficiency of an
electrolyzer unit because of its intricate reaction mechanism [1].
This review focuses on how electrolyte affects the HER in electrochemical water
splitting. Despite this emphasis, it is noteworthy that the OER imposes more significant
constraints on the overall process. The lower overpotentials observed for the HER, com-
pared to the OER, are primarily attributed to the comparatively sluggish kinetics of the
OER. Thermodynamically, a voltage as low as 1.23 V is theoretically ample for the elec-
trolytic splitting of water into O2 and H2 , because Eo O2/2H2O = 1.23 V and Eo 2H+/H2 = 0 V
in standard conditions. Nevertheless, it is evident that, at ∆E = 1.23 V, the current density is
observed to be zero [12]. Modern alkaline electrolyzers typically function at voltages above
1.8 V, with considerable rates of the HER and the OER occurring between 2.0 to 2.5 V.
As elaborated in [12], the OER mechanism on an oxidized metal electrode surface
should involve the formation of hydrogen peroxide (H2 O2 ) as an intermediate. This is
followed by the oxidation of H2 O2 to O2 , involving a cascading water oxidation process
from the oxidation state of oxygen (−2) in water to (−1) in peroxide, ultimately reaching 0
in a free gas:
2H2 O − 2e− H2 O2 + 2H+ Eo = 1.77 V (1)
H2 O2 − 2e− O2 + 2H+ Eo = 0.68 V (2)

The arrangement of the Eo values for Reactions (1) and (2) indicates that, once H2 O2 is
generated, it undergoes spontaneous oxidation to produce O2 . However, this process is
notably slow at lower electrochemical potential values. The formal equation for the OER is
derived by dividing the sum of these two reactions by 2:
H2 O − 2e− 1/2O2 + 2H+ Eo = 1.23 V (3)
while the process, actually, does not follow this path. Therefore, Reaction (1) with Eo = 1.77 V
should be considered to be the main energetic barrier in the H2 O-splitting process.
The study utilized a water photoelectrolysis cell with a Pt cathode and a Ti/(Ir-Ta)
oxide anode connected to an n-Si/Ni Schottky solar cell battery. When the illumination
on the solar cell was turned OFF, the cell voltage stabilized at 0.68 V, supporting the
suggested water-splitting mechanism involving an H2 O2 intermediate. Upon turning OFF
the illumination, electrolysis halts, and the Pt cathode potential remains temporarily at 0 V.
Simultaneously, the anode maintains the potential of the redox couple O2 /H2 O2 as per
Equation (2).
Water oxidation, thermodynamically feasible at 1.23 V, can be depolarized between
1.23 V and 1.77 V with the appropriate electrocatalysts. The mechanism of the electrocat-
alytic OER taking place on the Ni electrodes and involving the formation of metal surface
peroxide species has been proposed [16]. Based on experimental findings and existing
literature, it is proposed that, in alkaline conditions at E ≈ 1.5 V (RHE), there is a reversible
electrochemical generation of Ni(IV) peroxide described by the reaction: NiO(OH)2 +
2OH− NiOO2 + 2H2 O + 2e− . This reaction explains the underpotential O2 formation
from NiOO2 peroxide (with respect to Eo H2O2/H2O = 1.77V), as well as the observed low
dE/dlog(i) slope (<60 mV) at low anodic current densities, indicative of a two-electron
transfer process.
During photolytic water splitting on a semiconductor surface, a 1.23 eV photon breaks
one O–H bond in an H2 O molecule. To break both bonds, two such photons (equivalent to
~2.46 eV) are needed, similar to the energy released when one mole of H2 gas is burned in
O2 . This work can also be accomplished by two photons with energies ≥ 1.77 eV + 0.68 eV
or a single photon with energy ≥ 2.46 eV. In terms of energy, electrolytic and photolytic
water splitting incur similar costs. The low probability of the direct reaction in Equation (3)
could be attributed to nonlinearity, where two water molecules exchanging four electrons
contrasts with Equation (1), where only two electrons are involved, making the latter
pathway more probable due to the space-time synchronization in the electrochemical
reaction [12].
Amid the global energy crisis, there is a rising interest in the HER to produce pure
(green) hydrogen using renewable energy sources. Researchers are actively exploring new
and cost-effective catalysts for HER to make this process economically viable. The HER
volcano curves [17–19], based on Sabatier’s principle, are valuable tools in understanding
trends in HER activity, aiding in the search for optimal electrocatalysts by analyzing the
reaction rate against the free energy of adsorption for intermediates [2].
Depending on the type of electrolyte employed, water electrolysis can take place in
acidic, pH-neutral, or alkaline conditions. Equations (4) and (5) outline the corresponding
HER reactions in acidic and alkaline electrolytes, respectively:
2H+ + 2e− → H2 (4)
2H2 O + 2e− → H2 + 2OH− (5)

The mechanism of the HER, which is influenced by the pH of the solution [20], can be
summarized in acidic environments as follows (* is an empty adsorption site):
H+ + e− + * → Hads (6)
Hads + Hads → H2 + 2* (7)

H+ + Hads + e− → H2 + * (8)
In an alkaline media, the HER mechanism can be presented in a similar way:
H2 O + e− + * → Hads + OH− (9)
Hads + Hads → H2 + 2* (10)
H2 O + Hads + e− → H2 + OH− + * (11)

Within the above-presented mechanisms, * signifies an unoccupied active site on the
catalyst’s surface. The reaction is initiated with a Volmer step (Equations (6) and (9)), and
the intermediate species (Hads ) is subsequently eliminated from the surface via either the
Tafel reaction (Equations (7) and (10)) or the Heyrovsky reaction (Equations (8) and (11)).
The HER on Pt and PGMs is rapid and reversible at a low pH, but cost and scalability issues
demand alternative catalysts. Cheaper metals like Ni hold potential as alternatives to Pt
for the HER, but they exhibit lower performance and stability issues in acidic conditions.
In alkaline media, the HER is notably slower, even on Pt, mainly due to the sluggish H2 O
dissociation step (Equation (9)). PGMs still have excellent HER performance in alkaline
environments, but their activity declines by ~2 order of magnitude compared to acidic
media [21], emphasizing the impact of the electrolyte in the HER.
However, it is important to note that studies by [22,23] have challenged the classical
HER mechanism. In particular, [22] reexamined the mechanisms of a reversible HER and
HOR through thermodynamic analysis and a recent literature review. Contrary to the long-
standing assumption involving Had atoms as intermediates, the study proposed that the
adsorbed molecular ion (H2 + )ad serves as the intermediate in both HER and HOR reactions,
aligning better with contemporary experimental observations. Moreover, [24] analyzed
experimentally reported data with models which provide a quantitative match [25]. The
analysis suggests that the reversible electrochemical hydrogen evolution (H2 ER) occur-
ring in acidic, neutral, and alkaline aqueous solutions can be described by one common
reaction (Equation (14)), which involves an intermediate stage of the adsorbed hydrogen
molecular ion (H2 + ) instead of Had as postulated in the typical Volmer–Heyrovsky–Tafel
mechanism. The distinctive characteristics of this reaction are as follows: (i) it entails
the transfer of two electrons for each H3 O+ and OH− ion; (ii) the precursor of the H2
molecule is the molecular hydrogen ion (H2 + )ad , which forms during the transfer of the
first electron (Equation (12)), with the second electron transfer leading to the formation of
H2 (Equation (13)); (iii) the energy of hydration preserved within the H3 O+ ion is utilized
for the bond formation in the H2 molecule and accounts for the depolarization of the
H+ discharge from Eo H+/H = −2.106 V (SHE) to E > 0 V, known as the HUPD phenomenon
observed on Pt. Considering these factors, the formation of Had as an intermediate in the
HER/HOR appears to be both thermodynamically and kinetically unfavorable.
In the reversible region of the hydrogen evolution, theoretical analysis indicates two
possible slopes of potential vs. log(i) plots: 2.3 RT/F ≈ 60 mV and 2.3 RT/2 F ≈ 30 mV. This
aligns with findings in the literature on the electrocatalytic hydrogen evolution, serving
as evidence for the alternative mechanism described herein. Recent experimental results
on Pt electrodeposition [25] align with the presented analysis, providing support for the
mechanism, involving the formation of H2 + as an intermediate in the reversible hydrogen
evolution on Pt. As the transition to the irreversible hydrogen evolution occurs, a slowdown
in the formation of H2 + in the first electron transfer stage manifests, leading to an increased
slope of 2.3 RT/0.5 F ≈ 120 mV (here, R, F, and T represent the universal gas constant,
Faraday constant, and absolute temperature, respectively). The processes occurring at
E = 0 V (SHE) can be described by the following sequence of electrochemical reactions:
H3 O + + e − (H2 + )ad + OH− (12)

(H2 + )ad + e− H2 (13)

The overall reaction is:
(H2 + )ad
H3 O+ + 2e− H2 + OH (14)
Near the equilibrium potential, both processes (12) and (13) occur rapidly and re-
versibly and proceed simultaneously, leading to an overall two-electron process (14). This
process characterizes redox reactions on a Pt surface within specific rate limits in an RHE.
It plays a key role in determining the exchange current (i0 ) magnitude and the potential (E)
of the overall electrochemical process.
Numerous water electrolysis techniques have been studied and can be categorized
according to the electrolytes used. These methods encompass proton exchange membrane
electrolysis (PEMEL) and alkaline electrolysis, which includes both traditional alkaline
water electrolysis (AEL) and anion exchange membrane electrolysis (AEMEL) [2,7,13,26].
Although both AEL and PEMEL have attained high degrees of technological maturity [26],
it is still challenging to produce hydrogen on a large scale using water electrolysis due to
the high cost of PGM catalysts in acidic conditions and the low energy conversion efficiency
of non-PGM catalysts in alkaline conditions. Moreover, the local acidic environment in
PEMELs severely restricts the selection of electrocatalysts to a small subset of PGMs [27].
On the other hand, alkaline water splitting, employing a cost-effective KOH electrolyte,
enables the use of affordable non-PGMs such as Ni, offering advantages over PEMEL cells.
In practical applications, large-scale water electrolysis is carried out in concentrated alkalis,
utilizing stable and inexpensive Ni-based catalysts, whose decreased activity relative to Pt
is offset by their lower price [20].
The kinetics of the HER can be influenced by different factors, including the nature
and composition of the electrolyte, the crystal shape and orientation of the electrode (single-
crystal, polycrystalline, amorphous, etc.), and many other factors. This review will discuss
the effect of the nature and concentration of the electrolytes on the kinetics of the HER.
1.2. Importance of Studying the Kinetics of the HER

Based on the elementary processes (Equations (3)–(5)), it is conceivable to imagine
two potential mechanisms in acidic conditions, Volmer–Tafel and Volmer–Heyrovsky [28],
and the preferred mechanism depends on various factors, including the surface coverage
of Hads and the overpotential applied. In situations where the surface coverage is high,
there is a higher likelihood of the Volmer–Tafel mechanism occurring due to the increased
probability of the surface recombination step. Conversely, when the surface coverage is
low, the Volmer–Heyrovsky mechanism is favored [2]. The Volmer–Tafel pathway is more
common at low overpotentials, while the Volmer–Heyrovsky becomes more prevalent as
the overpotential increases [29]. The above-mentioned mechanisms can result in three
possible rate-determining steps (RDSs): Volmer, Heyrovsky, and Tafel. Both mechanisms
exhibit an exponential increase in the catalytic current with overpotential. Still, the rate of
increase differs for different RDSs, allowing for the identification of the RDS and the surface
mechanism of a catalyst [28]. Previous studies [30–34] have suggested that the Volmer step
is the RDS for the kinetics of the HER/HOR on polycrystalline Pt surfaces. Conversely,
some other studies [35,36] suggest that the Heyrovsky step controls the kinetics of the HER.
The Tafel slope provides information about the RDS and the plausible HER mechanism,
specifically related to the electron-transfer kinetics in the catalytic reaction. A smaller Tafel
slope indicates faster electrocatalytic kinetics, leading to a higher current density (j) with
a lower overpotential. The exchange current density (j0 ) refers to the charge transfer
rate under equilibrium conditions. A greater j0 signifies an accelerated charge transfer
rate and a diminished reaction barrier [28]. Thus, a better electrocatalyst typically has a
lower Tafel slope and a higher j0 [37]. In the HER potential region at 25 ◦ C, different Tafel
slopes are theoretically predicted based on the RDS, i.e., −120 mV dec−1 , −30 mV dec−1 ,
and −40 mV dec−1 for the Volmer, Tafel, and Heyrovsky limiting reactions, respectively.
Typically, a Tafel slope of −120 mV dec−1 is observed on most materials at practical
current densities. This finding is attributed to the slow discharge of protons or the sluggish
electrochemical desorption of Hads atoms. However, in acidic environments where the
Volmer step is exceptionally rapid, PGMs tend to exhibit a lower Tafel slope of −30 mV
dec−1 . While the literature commonly associates a Tafel slope of −120 mV dec−1 with the
Volmer step for the HER, Shinagawa et al. showed that this slope can also be obtained
when the Heyrovsky step is the RDS at high Hads coverage (>0.6) [36].
Moreover, there is a scenario where different steps proceed at a similar rate, making the
Tafel slope analysis uncertain [21]. Watzele et al. discussed the challenges and uncertainties
in understanding the HER. The authors used electrochemical impedance spectroscopy to
study the relative contributions of two pathways (Volmer–Heyrovsky and Volmer–Tafel) to
the HER at different electrode potentials and pH values. Their results showed that both
pathways contribute similarly to the reaction, and neither dominates [38]. Electrocatalytic
kinetics, unlike outer-sphere reactions, are intricate due to adsorbed intermediates. The
Butler–Volmer equation must account for the variable surface coverage of these species
influenced by the electrode potential, posing challenges in the Tafel slope interpretation, no-
tably in the HER and similar processes. Thus, not only is the HER mechanism identification
based on the Tafel slope difficult, it can also be very misleading.
1.3. Definition and Types of Electrolytes Used in HER Studies

Various electrolytes are used for HER studies. They can differ by pH (acidic, neutral,
or alkaline) or solvent (such as organic solvents or ionic liquids). The choice of electrolytes
significantly impacts the efficiency of the HER [15]. The majority of the research on
the HER mechanisms and the activity of different materials has been conducted under
kinetically preferred, extremely acidic [17,39–42], and alkaline aqueous conditions [42–47]
while there has also been significant attention on studying the HER under near-neutral
pH conditions [48–52]. Acidic electrolytes used for the HER include H2 SO4 [17,18,53,54],
HCl [55,56], and HClO4 [42,55,57,58]; and the most commonly used alkaline electrolytes
include NaOH [59,60] and KOH [19,42,45,55,57,61–67]. At the same time, the use of LiOH
can also be found in the literature [55]. Besides the traditional liquid electrolytes, other
types of electrolytes, such as solid electrolytes and ionic liquids (ILs), are also investigated
for the HER. ILs are utilized in electrochemical systems for an efficient HER due to their
exceptional properties, such as low vapor pressure, high electrical conductivity, and a wide
variety of functional groups [15]. For example, Amaral et al. [68] studied the impact of
adding an ionic liquid (IL) ([Emim][MeSO3 ]) to a Pt cathode in an 8 M KOH solution at
temperatures from 25 to 85 ◦ C. The IL addition exhibited a catalytic effect, increasing j0 and
reducing overall impedance up to 45 ◦ C. The activation energy for the HER in the IL-added
KOH was 10 kJ mol−1 compared to the IL-free KOH solution.
1.4. Significance of Electrolytes in HER Kinetics

In general, the HER is performed in highly acidic or highly alkaline electrolytes, and
the nature of the electrolyte plays a significant role in the kinetic of the HER. Due to the
availability of higher concentrations of H3 O+ ions, the HER on PGMs in acidic solutions
is remarkably fast. However, its efficiency is limited by the diffusion of hydrogen ions
from the bulk of the solution to the electrode–electrolyte interface where the concentration
is not sufficiently high [42]. Furthermore, the acidic environment significantly limits
the catalyst options to only a few scarce and costly PGMs [27]. Conversely, the HER in
alkaline electrolytes is relatively slow, but it allows us to use affordable non-PGMs. Besides
strongly acidic/alkaline electrolytes, the HER can also occur in neutral and near-neutral
electrolytes. These electrolytes provide benefits like reduced corrosion and a wider range
of electrocatalysts without the need for specialized membranes or acid/alkali-resistant
catalysts [69,70]. Furthermore, neutral environments facilitate the utilization of seawater
as an electrolyte and the desegregation of metal-based electrocatalysts with biocatalysts
to produce biofuels [2]. Merrill et al. [71] found that protonated weak acids in microbial
electrolysis cell (MEC) solutions affect the HER through weak acid catalysis and reducing
solution resistance. The study emphasized the importance of specific buffers in optimizing
the MEC efficiency across different pH ranges, with phosphate and acetate working better
in acidic conditions and carbonate at a higher pH due to the increased conductivity.
Recent research has demonstrated that the interactions between the electrolyte and the
electrocatalyst significantly influence the electrocatalytic properties. The electrolyte’s im-
pact on the electrochemical reactions occurs through two mechanisms: (i) via the chemisorp-
tion of adsorbents in the inner Helmholtz layer involving the electron transfer, and (ii)
through weak van der Waals interactions between the electrode and spectator (supporting)
ions in the electrolyte at the outer Helmholtz layer [72,73]. The kinetics of the HER in an
aqueous medium are typically influenced by two adsorbates: Had in acidic conditions and
OHad in alkaline conditions. For example, Strmcnik et al. found that OHad plays a crucial
role in the HER over Had for Pt in an alkaline medium [50]. However, conflicting reports
have led to ongoing debates in this regard [74].
For a long time, the hydrogen binding energy (HBE) of the metal catalyst surface
or the energy of the M–H bond (∆EM-H ) were outlined as a factor influencing the HER
rate, starting with the classical works of Trassati studying the HER in acidic media. Sheng
et al. experimentally demonstrated that the hydrogen desorption peaks of underpotential
deposited hydrogen (HUPD ) on Pt(100) and Pt(110) are directly linked to the metal HBE and
are pH-dependent [75]. Increasing pH levels led to an increased HBE on Pt, resulting in a
decrease in Pt’s HER activity. Koper et al. demonstrated that spectator ions such as alkali
metal cations, viz., Li+ , Na+ , K+ , and Cs+ , have the ability to weaken the metal–OHad bond
(M-OHad ), resulting in an elevation of the interfacial pH and a subsequent positive shift
in the HUPD desorption peak [76]. Later on, it was found that not only the pH values of
the electrolyte but also the co-adsorption of alkali metals such as K are responsible for the
positive shift in the HUPD desorption peak of Pt by weakening the Pt-OHad bond. Recent
research indicates that aqueous electrolytes containing alkali metal cations, specifically
Li+ , can effectively enhance various electrochemical reactions, including those in batteries,
carbon dioxide reduction, and nitrogen reduction [73].
The use of Li+ -containing aqueous electrolytes is not yet commercialized, making
HER suppression necessary in certain processes [77]. Suo et al. discovered that highly con-
centrated lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-based aqueous electrolytes
(>5 M) can achieve a water-in-salt condition and enhance the water stability window to
~2.9 V [78]. However, at higher LiTFSI concentrations, TFSI− ions can split to form F– ,
which creates an LiF layer on the active electrode (stainless steel), selectively blocking the
diffusion of H+ ions. Guha et al. discovered that the observed phenomenon in the presence
of Li+ goes beyond the formation of LiF and is independent of the supporting anion (TFSI− ),
particularly when working with high Li+ concentrations rather than low concentrations as
in previous reports [79]. They found that Pt electrodes suppress the HER at all pH values,
while, for bulk gold (Au), HER activities are enhanced with Li+ . The study suggested that
the M/Li+ interaction plays a significant role in this phenomenon, and the enhanced H2 (g)
production with Au was confirmed using gas-chromatography-based quantifications.
2. Influence of Electrolyte Composition on HER Kinetics

2.1. Effect of Electrolyte pH on HER Kinetics
The influence of the electrolyte pH on the rate of the HER was overlooked due to the
experimental limitations in assessing rapid kinetics in acidic media. Nevertheless, it is now
evident that pH strongly affects the HER, particularly on highly active metals. For instance,
when moving from pH = 0 to pH = 13, the HER activities of Pt, Ir, and Pd drop by factors of
210, 120, and 90, respectively [43,80]. On the other hand, non-PGM electrodes, such as Au,
Ni, or Cu, experience a lesser impact, with a 10-fold reduction in HER activity [17,19,80].
Additional studies conducted in neutral solutions have shown that the decrease in activity
directly correlates with the pH level [75]. Experimental findings show that the HER activity
of various electrocatalysts progressively declines with the rise in pH [50]. A significant

decrease in HER activity for Pt(111), Au(111), and polycrystalline Ir (Irpc ) was observed
with increasing pH (pH = 1 to 13) [81]. Au(111) displayed higher overpotentials than
Pt(111) and Irpc at the same current density in acidic pH, attributed to the mass transport
of reactive H3 O+ species regulating the HER [49]. However, above pH = 5 and certain
potentials, metal polarization curves became pH-independent, suggesting the H2 O to H2
transformation dominated the HER currents. Thus, the main difference between the HER
in alkaline and acidic media is that the HER in alkaline solutions is limited by a sluggish
water dissociation step (Equation (6)) [50].
Examining the impact of surface-dependent kinetic rates is another way to investigate
how the pH of the electrolyte affects the HER. In particular, while the activity of Pt low-
index single-crystal surfaces varies only slightly in acidic media, it varies significantly in
alkaline solutions [39,44,82]. According to Danilović et al. [83], the highly defected Pt(110)
exhibits higher activity compared to the relatively “perfect” Pt(111). Moreover, the variation
in activity is explained by the fact that the adsorption of the hydroxyl and HUPD species is
influenced by the structure of the crystal surface, which ultimately impacts the formation
of the electroactive intermediate, HOPD [45]. For a more thorough understanding of the
HER’s structure–activity relationship, Marković et al. [81] have conducted a comparative
study between the HER activity of Pt(111) and Pt(111) decorated by electrochemically
deposited Pt islands (Pt-islands/Pt(111)). In alkaline media, the Pt-islands/Pt(111) surface
exhibited a five- to six-times-higher HER activity compared to the pristine Pt(111), while
in acidic media, the enhancement was only around 1.5 times. The pH effect shows that
low-co-ordinated single-crystal Pt atoms play a crucial role in increasing the rate of the
HER in alkaline solutions, promoting the dissociative adsorption of water [81].
In the current literature, several prevailing hypotheses explain why HER kinetics are
slower in alkaline solutions than in acidic ones:
(i) The HBE is pH-dependent [19,75,84]. This concept has helped to explain numerous
experimental findings, even though some inconsistencies still exist [81,84,85]. For
illustration, if the HBE were to increase, it would account for the positive potential
shift of the HUPD on the PGM electrodes when they change from an acidic to an
alkaline electrolyte. Nevertheless, despite demonstrating considerably lower HER
activity in alkaline electrolytes than in acidic ones, the Pt(111) surface remains largely
unaffected by this shift caused by the HUPD [80,86,87]. Furthermore, if there were a
universal increase in the HBE with pH, it would enhance the HER electrocatalytic
activity of metals that weakly bind hydrogen (such as Au). However, this contradicts
the experimental observations [80].
(ii) The proton donor (H3 O+ or H2 O) is pH-dependent [50]. In other words, the pro-
ton donor can switch from H3 O+ in an acidic environment to H2 O in an alkaline
environment.
(iii) At the electrode|electrolyte interface, there is a pH-dependent water reorganization
energy. According to Koper et al. [88], the water-reorganization energy related to
the proton–electron transfer would be higher because interfacial fields are stronger
in an alkaline environment. Rossmeisl et al. [89] initiated an attempt to address the
pH in the density functional theory (DFT) calculation and, applying the scheme to
the Pt(111)|electrolyte(water) interface as an example, they have observed that the
adsorbate coverage and water orientation were affected by the pH [89]. Recent studies
by Rossmeisl et al. have associated the reduction in HER activity at a high pH with
changes in the configurational entropy of the proton as it crosses the outer Helmholtz
plane [90]. Cheng et al. [91] carried out full solvent quantum mechanics molecular
dynamics (QMMD) simulations to explicitly simulate the water/Pt(100) interface at
an applied voltage (U) from +0.29 V to −0.46 V, which is equivalent to a pH from 0.2
to 12.8 at U = 0.3 V (RHE). The study deduced that the pH-dependent HBE on the
noble metal is mostly caused by changes in water adsorption. They discovered that
Hydrogen 2023, 4, FOR PEER REVIEW 9

to 12.8 at U = 0.3 V (RHE). The study deduced that the pH-dependent HBE on the
noble metal is mostly caused by changes in water adsorption. They discovered that
the electrode exhibited a tendency to repel water as the applied voltage was made
the
moreelectrode exhibited
negative, which, in a tendency to repel
turn, boosted water as the
the hydrogen applied voltage was made
binding.
more negative, which, in turn, boosted the hydrogen binding.
The HER mechanism in neutral solutions is proposed to be similar to that of the al-
Themedia,
kaline HER proceeding
mechanismthrough
in neutral thesolutions
adsorption is step
proposed to be(6)),
(Equation similar to that
followed by of
thethe
de-
alkaline media, proceeding through the adsorption step (Equation (6)), followed
sorption steps (Equations (7) or (8)). In near-neutral pH with typical supporting electro- by the des-
orption steps (Equations (7) or (8)). In near-neutral pH with typical supporting electrolytes
lytes like Na2SO4 or NaClO4, the HER relies on water as the primary reactant for significant
like Na2 SO4 or NaClO4 , the HER relies on water as the primary reactant for significant
hydrogen production. Due to the reduced hydronium ion activity in these circumstances,
hydrogen production. Due to the reduced hydronium ion activity in these circumstances,
reactant mass-transport flux becomes slower than the surface hydronium ion reduction
reactant mass-transport flux becomes slower than the surface hydronium ion reduction
rate. As a result, in unbuffered near-neutral-pH electrolyte solutions, a significant amount
rate. As a result, in unbuffered near-neutral-pH electrolyte solutions, a significant amount
of overpotential is needed to achieve greater current densities than in acidic or alkaline
of overpotential is needed to achieve greater current densities than in acidic or alkaline pH
pH conditions [92]. In pH-neutral electrolytes, the HER process involves a two-step re-
conditions [92]. In pH-neutral electrolytes, the HER process involves a two-step reduction
duction process. In contrast, in strongly acidic or alkaline electrolytes, the reduction oc-
process. In contrast, in strongly acidic or alkaline electrolytes, the reduction occurs in a
curs in a single step with H3O+ ions or H2O molecules, respectively [93]. During the initial
single step with H3 O+ ions or H2 O molecules, respectively [93]. During the initial reduction
reduction phase of the HER, the main reactants are H3O+ ions, and this occurs at low ca-
phase of the HER, the main reactants are H3 O+ ions, and this occurs at low cathodic over-
thodic overpotentials.
potentials. As the overpotential
As the overpotential increases, the increases,
HER processthe HER process
becomes becomes diffusion-
diffusion-controlled,
controlled, where a constant current is observed [52]. The second
where a constant current is observed [52]. The second reduction phase takes place reduction phase takes
at higher
place at higherduring
overpotentials, overpotentials,
which the during
principalwhich the principal
reactants in the HER reactants
change in fromtheHHER + change
3 O ions to
from H 3O+ ions to H2O molecules, leading to a steady rise in the reduction current [69].
H2 O molecules, leading to a steady rise in the reduction current [69]. For instance, the HER
For instance, the
electrocatalytic HER electrocatalytic
performance of Pt in theperformance
pH range of 5oftoPt in thenot
9 does pHalign
range of 5the
with to predicted
9 does not
align with the predicted shift in the thermodynamic potential (i.e.,
shift in the thermodynamic potential (i.e., −59 mV per pH unit) [51]. The Mayrhofer −59 mV per pH unit)
group [48] discovered that, in unbuffered or inadequately buffered electrolytes, buffered
[51]. The Mayrhofer group [48] discovered that, in unbuffered or inadequately the pH
electrolytes,
near electrodethe pH near
surfaces electrode surfaces
significantly deviatessignificantly
from the bulk deviates frompH,
electrolyte the bulk electrolyte
particularly in
pH,range
the particularly
of pH 4 in
to the range of
10 (Figure 1).pH 4 to observations
These 10 (Figure 1).suggest
These observations
that the kineticssuggest
of thethat
HERthe
inkinetics of theconditions
pH-neutral HER in pH-neutral conditions behave uniquely.
behave uniquely.
Figure1.1. Current
Figure Currentdensity–surface
density–surfacepH pHrelation obtained
relation by by
obtained cyclic voltammetry
cyclic (rotation
voltammetry rate:rate:
(rotation 1600
rpm;rpm;
1600 scanscan
rate: rate:
10 mV10 smV
−1) in H2-saturated, unbuﬀered solutions of bulk pH values equal to (□) 1,
s−1 ) in H2 -saturated, unbuffered solutions of bulk pH values equal
(▽) 4, (○) 7, (Δ) 10, and (◊) 13. The solid lines denote the predictions for the corresponding solutions
to () 1, (5) 4, (#) 7, (∆) 10, and (♦) 13. The solid lines denote the predictions for the corresponding
as derived from Equation (5). The effective surface pH is indicated at the top and by the underlying
solutions as derived from Equation (5). The effective surface pH is indicated at the top and by the
color scheme. Reproduced from/Reprinted from Ref. [48] with permission from Elsevier.
underlying color scheme. Reproduced from/Reprinted from Ref. [48] with permission from Elsevier.
Hydrogen
Hydrogen 2023,
2023, 4 4, FOR PEER REVIEW 10
785
Furthermore,Takanabe’s
Furthermore, Takanabe’sresearch
researchteam
teamuncovered
uncovered that
that thethe HER
HER processes
processes in in near-
near-pH-
pH-neutral
neutral solutions
solutions are influenced
are influenced by nature
by the the nature of reactants,
of the the reactants,
the the state
state of the
of the electro-
electrolytes
lytes (buffered
(buffered or unbuffered),
or unbuffered), and their and their concentrations
concentrations [51,52,94].
[51,52,94]. They investigated
They investigated the
the relation-
relationship
ship between between
the HER theandHER
the pHandusing
the pH usingunbuffered
various various unbuffered
0.5 M Na20.5
SO4Msolutions.
Na2SO4 solu-They
tions. that
found Theythe
found
HERthat the HER
activity activity
is based on is
thebased on the
activity of H +
activity of rather
H3O+ ions
thanrather than
3 O ions the nature
the
of nature
the of the supporting
supporting electrolyteelectrolyte
(Figure 2).(Figure 2). Depending
Depending on the theoretical
on the theoretical diffusion-
diffusion-limited
limiteddensity,
current currentthe
density,
authorsthecategorized
authors categorized the HER
the HER activity intoactivity intoregions:
three pH three pH regions:
acidic (1–5),
acidic (1–5),
neutral (5–9),neutral (5–9), and
and alkaline alkaline
(9–13) (9–13)
[51]. The [51]. The
neutral neutral
region was region
found towas found
have to have
insufficient
+
Hinsufficient H3O+ ions,thelimiting the HER activity.
3 O ions, limiting HER activity.
Figure 2. Linear sweep voltammograms for HOR using (a) Pt disk and (b) Pt/C electrodes at a rota-
Figure 2. Linear sweep voltammograms for HOR using (a) Pt disk and (b) Pt/C electrodes at−1 a
tion rate of 3600 rpm in the positive direction. Conditions: H2, Na2SO4 (0.5 m), 298 K, and 50 mV s .
rotation
Reprintedrate of 3600
from rpmwith
Ref. [51] in the positive from
permission direction.
Wiley.Conditions: H2 , Na2 SO4 (0.5 m), 298 K, and
− 1
50 mV s . Reprinted from Ref. [51] with permission from Wiley.
Yet, the supply of H3O++ ions can be enhanced by buffered electrolytes, which helps
Yet, the supply of H3 O ions can be enhanced by buffered electrolytes, which helps
overcome the limited H3O+ ion availability near electrode surfaces [52,92,95]. Research has
overcome the limited H3 O+ ion availability near electrode surfaces [52,92,95]. Research has
been focused on improved an neutral-pH performance using buffered solutions [48,49]
been focused on improved an neutral-pH performance using buffered solutions [48,49] such
such as phosphate, borate, and carbonate [71,96–98], yielding onset potentials similar to
as phosphate, borate, and carbonate [71,96–98], yielding onset potentials similar to acidic
acidic and alkaline conditions [49,71]. Koper et al. [99] have investigated the HER in bi-
and alkaline conditions [49,71]. Koper et al. [99] have investigated the HER in bicarbonate-
carbonate-containing electrolytes on Au and Pt electrodes and observed an enhanced HER
containing electrolytes on Au and Pt electrodes and observed an enhanced HER rate with
rate with a bicarbonate buffer despite maintaining a constant bulk pH. Additionally, there
a bicarbonate buffer despite maintaining a constant bulk pH. Additionally, there was a
was a notable alteration in the reaction mechanism, with the Tafel Slope in bicarbonate
notable alteration in the reaction mechanism, with the Tafel Slope in bicarbonate mirroring
mirroring that in acidic conditions (100 mV dec−1 on Au and 40 mV dec−1 on Pt). The ob-
that in acidic conditions (100 mV dec−1 on Au and 40 mV dec−1 on Pt). The observed result
served result stems from the controlled pH near electrode surfaces due to ongoing reac-
stems from the controlled pH near electrode surfaces due to ongoing reactions and buffering
tions and buffering effects. On the other hand, some studies contend that the weak acid
effects. On the other hand, some studies contend that the weak acid itself, e.g., phosphate
itself, e.g., phosphate species (H2PO4− and HPO42−), is likely the reactant in buffered con-
species (H2 PO4 − and HPO4 2− ), is likely the reactant in buffered conditions [71,94,100].
ditions [71,94,100]. While it remains uncertain if weak acid ions directly interact on the
While it remains uncertain if weak acid ions directly interact on the surface, the HER
surface, the HER current on a Pt catalyst is primarily determined by the mass transport of
current on a Pt catalyst is primarily determined by the mass transport of a proton source
a proton source (like phosphate ions) to the vicinity of the catalyst surface [92,94]. The
(like phosphate ions) to the vicinity of the catalyst surface [92,94]. The HER activities in
HER activities in pH-neutral and alkaline conditions are significantly different, even
pH-neutral and alkaline conditions are significantly different, even though they are both
though they are both thought to be influenced by the water dissociation as the RDS. Some
thought to be influenced by the water dissociation as the RDS. Some studies suggest that
studies suggest that the HER activity is better in neutral electrolytes, while others claim
the HER activity is better in neutral electrolytes, while others claim the opposite.
the opposite.
Yan and colleagues proposed that HBE can serve as the sole factor to account for the
Yan and colleagues proposed that HBE can serve as the sole factor to account for the
gradual reduction in the HER activity observed across PGM catalysts in different buffer
gradual reduction in the HER activity observed across PGM catalysts in different buffer
electrolytes with a pH ranging from 0 to 13 [75,84]. According to them, HBE is higher
electrolytes with a pH ranging from 0 to 13 [75,84]. According to them, HBE is higher in
in higher-pH electrolytes, resulting in intermediate HER kinetics in neutral electrolytes.
Additionally, they recommended that OH− can tune the HBE and affect HER activity. Shao
et al. [101] conducted a study using surface-enhanced infrared absorption spectroscopy

and found that the HBE of Pt catalysts is influenced by the modified electric field, Hads
coverage, and Pt-H2 O, as well as Hads -H2 O interactions, leading to a weakened HBE with
increased pH levels; this can cause slower reaction kinetics and lower HER activity in high-
pH environments. However, the HBE descriptor is insufficient to explain the HER catalytic
behavior on well-defined Pt(111) surfaces [88]. According to Marković and Koper, the HER
catalytic behavior on such surfaces is also determined by the presence of adsorbed hydroxyl
molecules [47,50,88]. Marković et al. [81] suggested that, in alkaline environments, the HER
and HOR require different types of sites for the Hads and OHads , and the presence of OHads
can affect the kinetics by rivalling for the same surface sites (blocking effect) or modifying
the adsorption energy (energetic effect) of the active intermediates [50,81]. They proposed
that the activity of the HER in alkaline solutions can be enhanced by carefully balancing
the rate of H adsorption and OH desorption. Despite debates over the precise mechanisms
involved, the combination of Ni(OH)2 (for the strongest OHads bond strength) with Pt (for
the optimal Hads adsorption free energy, ∆ads GH ) has been found to enhance the activity of
the HER in alkaline electrolytes significantly. This bi-functional tuning approach has also
been favorably applied to pH-neutral solutions, suggesting that it is a viable method for
speeding HER kinetics in pH-neutral solutions [69,102].
2.2. Impact of Different Cations and Anions on HER Kinetics

Researchers are working to improve catalyst activity by adjusting covalent adsorbate–
surface interactions through surface electronic structure features. A current focus in electro-
catalysis research is understanding the impact of spectator electrolyte species on electrode
catalytic activity. In recent times, numerous instances of catalysts have been observed to
exhibit catalytic activity that depends on cations [83] and the pH [57,61,84]. Recent research
reveals that apparently inactive components in electrolytes have a significant impact on
catalytic performance. Specifically, alkali metal cations (Li+ to Cs+ ) in high-pH aqueous
electrolytes can cause notable changes in the reaction turnover frequency through noncova-
lent interactions with water molecules, spectator ions, surface adsorbates, and electrified
interfaces [103]. Furthermore, the catalytic activity of Pt for HOR, ORR, and methanol
oxidation, at 0.9 V versus RHE, is found to be cation-dependent, following the order of Li+
<< Na+ < K+ < Cs+ [104]. Moreover, the kinetics of HER is found to be strongly affected by
the nature of the cation, with Li+ having the most significant effect [72]. These observations
suggest that the chemical composition of electrolytes presents promising opportunities
to tune noncovalent interactions and solvation environments at the electrified interface,
potentially leading to significant changes in catalytic activity and selectivity.
Diverse studies have explored the impact of different alkali metal cations, including
Li+ , Na+ , K+ , and Cs+ , on the inherent HER performance of noble metals like Pt and Au.
However, these reports often present conflicting findings, while investigations on non-noble
metals remain scarce [105–107]. The presence of Li+ cations in the electrolyte was found to
have a substantial impact on the HER, especially in the presence of surface oxophilic groups,
surpassing the benefits of surface decoration with M(OH)2 [46]. According to Subbaraman
et al. [46], Li+ has the potential to boost the inherent HER performance of Pt-Ni(OH)2
composites, while the presence of Li+ had no effect on the HER for Pt alone. The authors
explained that the edges of Ni(OH)2 play a key role in water dissociation, which was
further amplified by the introduction of Li+ . However, the reason for (Li+ )’s ineffectiveness
in the presence of Pt alone remained unclear, and the HER enhancement phenomenon was
restricted to an alkaline environment. Recently, Liu et al. [108] proposed that Li+ facilitates
the elimination of adsorbed OHad from the double layer, thereby augmenting the intrinsic
HER activity of the Pt-Ni(OH)2 system.
Xue et al. [109] studied the role of different alkali-metal-cation-containing electrolytes
in the HER activity of the Pt(pc), Pt(111), Pt(221), Ir(111), Au(111), and Ag(pc) electrodes.
The study showed that the HER activity pattern of all the Pt-electrodes and that of Ir(111),
regardless of their surface structure, was fairly linked to the hydration energy of the alkali
Xue et al. [109] studied the role of different alkali-metal-cation-containing electrolytes

Hydrogen 2023, 4 in the HER activity of the Pt(pc), Pt(111), Pt(221), Ir(111), Au(111), and Ag(pc) electrodes. 787
The study showed that the HER activity pattern of all the Pt-electrodes and that of Ir(111),
regardless of their surface structure, was fairly linked to the hydration energy of the alkali
metal cations
metal cations ininthe
theelectrolyte,
electrolyte,following
followingthe sequence:LiLi++>> Na
thesequence: Na++ >> K++ >> Rb
Rb++>>Cs
Cs+.+ .This
This
pattern was
pattern was reversed
reversed for the Au(111) and Ag(pc) electrodes electrodes (Figure
(Figure 3).3). These
Thesefindings
findings
prove that
prove that the presence
presenceof ofalkali
alkalimetal
metalcations
cations indeed
indeedinfluences
influencesthethe
HER HERperformance
performance of
metal
of metalelectrodes,
electrodes, with variations
with of ~4
variations of times between
~4 times electrolytes
between containing
electrolytes Li+ and
containing Li+Cs +.
and
Cs +
It was
. Itproposed
was proposed that the observed
that influence
the observed may be may
influence attributed to non-covalent
be attributed interac-
to non-covalent
tions between
interactions alkalialkali
between metalmetal
cations nearnear
cations the the
catalytic centers
catalytic and
centers andthethe
adsorbed
adsorbedreaction
reaction
intermediates
intermediates at the electrode surface, or it could be due to the co-adsorption ofmetal
electrode surface, or it could be due to the co-adsorption of metal
cations onto
cations onto the electrode surface [72,109].
[72,109]. The
Thepresence
presenceof ofcations
cationsfacilitates
facilitatesthe
theremoval
removal
of OH
of OHad ad from the OHad ad-(H O)-AM+ +adduct,
-(H22O)-AM adduct,resulting
resultingininhigher
higherHERHERactivity
activitywith
withsmaller
smaller
and more
and more acidic
acidic alkali cations [110].
[110]. Weber
Weber et et al.
al. [72]
[72]also
alsofound
foundthat
thatan anenhanced
enhancedactivity
activity
with LiOH
with LiOH isis linked
linked to a lower activation
activation energy
energy compared
comparedto tothe
theactivity
activityobserved
observedwith with
NaOH and
NaOH and KOH
KOH electrolytes.
Figure 3. (a) The HER current densities of Ir(111) in H2-saturated alkaline solutions at −0.05 V vs.
Figure 3. (a) The HER current densities of Ir(111) in H2 -saturated alkaline solutions at −0.05 V vs.
RHE. The HER activity decreases from LiOH to CsOH, similar to that of Pt. (b) The HER current
RHE. The HER activity decreases from LiOH to CsOH, similar to that of Pt. (b) The HER current
densities of Au(111) and Ag(pc) in Ar-saturated alkaline solutions at −0.65 V vs. RHE. The activity
densities of Au(111)
trend is reversed and Ag(pc) with
in comparison in Ar-saturated alkaline
Pt and Ir. (c) The HERsolutions −0.65 of
currentatdensity V vs. RHE.in
Au(111) The activity
H2-satu-
trend
rated isalkaline
reversed in comparison
solutions at −0.65with
V vs.PtRHE.
and Ir. (c) The HER
Reprinted fromcurrent density
Ref. [109] withofpermission
Au(111) infrom
H2-saturated
Wiley.
alkaline solutions at −0.65 V vs. RHE. Reprinted from Ref. [109] with permission from Wiley.
Huang et al. [111] used a classical molecular dynamics (MD) simulation to investigate
Huang
the effect of et al. [111] used a classical molecular
structure-making/breaking cations ondynamics
the kinetics (MD) simulation
of the HER/HOR to investigate
of Pt(111)
the effect
in the pHofrange
structure-making/breaking
from 1 to 14. They observed cations onthe
that thecations
kineticsaffected
of the HER/HOR
the kinetics,ofwith
Pt(111)
j0
in the pH range from 1 to 14. They observed that the cations
increasing in the order Cs < Rb < K < Na < Li . Based on this study, electrolytes with
+ + + + + affected the kinetics, with
jlarger
0 increasing in the order Cs+ < Rb
(more structure-breaking)
+ < K+ < Na+ < Li+ . Based on this study, electrolytes
cations have more surface-bound cations than those with
with larger
smaller (more
(more structure-breaking)
structure-making) cations
cations, havetomore
leading surface-bound interfacial
a cation-dependent cations than those
hydro-
with smaller (more structure-making) cations, leading to a cation-dependent
gen-bonding network. The resulting variations in interfacial water structure can influence interfacial
hydrogen-bonding
the effective dielectric network.
properties Theandresulting variations
fluctuations, affectingin interfacial water structure
solvent reorganization energycan
influence
(Figure 4).the effective
Figure dielectric
4a shows thatproperties
larger cations and(Cs
fluctuations,
+) lead to the affecting
removal solvent reorganization
of water molecules
energy (Figure 4). due
Figure + ) lead to the removal of water
from the interface to a4astrong
shows that largerinteraction.
ion–surface cations (CsConversely, a stable interfacial
molecules
water layerfrom the interface
is formed due tocations
with smaller a strong (Liion–surface
+) (Figure 4b). interaction.
By applying Conversely,
the Born amodel
stable
interfacial water layer is formed with smaller cations (Li + ) (Figure 4b). By applying the Born
of reorganization energy and reaction entropy, the interfacial static dielectric constant was
model of reorganization
estimated to be notably lowerenergythan and in
reaction entropy, the
bulk electrolyte, interfacial
with the order static dielectric
of increase constant
being Li+
was estimated to be notably lower than in bulk electrolyte,
< Na < K < Rb < Cs on the negatively charged Pt RDE. This study suggests that, as
+ + + + with the order of increase being
Li + < Na+ < K+ < Rb+ < Cs+ on the negatively charged Pt RDE. This study suggests that, as
cations with a stronger structure-breaking tendency (e.g., Cs+) concentrate and partially
cations
desolvatewithat athe
stronger structure-breaking
electrified interface, this leadstendency Cs+ ) concentrate
(e.g., static
to higher and partially
dielectric constants, in-
desolvate at the electrified
creased reorganization interface,
energy, and this leads to higher
an elevated entropic static dielectric
barrier for theconstants,
formation increased
of Had
reorganization
from H2O, and,energy, and an
ultimately, elevated
reduces the entropic
kinetics ofbarrier for the formation of Had from H2 O,
the HER/HOR.
and, ultimately, reduces the kinetics of the HER/HOR.
Hydrogen 2023,
788
Figure 4.
Figure 4. The
The role
role of
of spectator
spectator ions,
ions, contained
contained inin the
the electrolyte,
electrolyte, in
in modifying
modifying the
the outer
outer Helmholtz
Helmholtz
layer (OHL) structure of the electrode/electrolyte interface. Schematic illustration (a) shows that
layer (OHL) structure of the electrode/electrolyte interface. Schematic illustration (a) shows that
larger cations (Cs+) lead to the removal of water molecules from the interface due to strong ion–
larger cations (Cs+ ) lead to the removal of water molecules from the interface due to strong ion–
surface interaction, while (b) demonstrating the formation of a stable interfacial water layer with
surface
smaller interaction,
cations (Li+).while (b) demonstrating
According to Ref. [111]. the formation of a stable interfacial water layer with
smaller cations (Li+). According to Ref. [111].
Monteiro et al. [112] investigated the influence of cation type and concentration on
Monteiro et al. [112] investigated the influence of cation type and concentration on
HER kinetics on Pt and Au electrodes. They found that weakly hydrated cations (e.g., K++)
HER kinetics on Pt and Au electrodes. They found that weakly hydrated cations (e.g., K )
promoted the HER on gold only at low overpotentials, while strongly hydrated cations
promoted the HER on gold only at low overpotentials, while strongly hydrated cations (e.g.,
(e.g., Li+) facilitated the HER at higher overpotentials (more alkaline pH). The same pat-
Li+ ) facilitated the HER at higher overpotentials (more alkaline pH). The same pattern was
tern was observed for Pt, but weakly hydrated cations inhibited the HER early at lower
observed for Pt, but weakly hydrated cations inhibited the HER early at lower alkalinity
alkalinity and cation concentrations. Weakly hydrated cations (K+) are proposed to stabi-
and cation concentrations. Weakly hydrated cations (K+ ) are proposed to stabilize the
lize the transition
transition state of the state of the
water water dissociation
dissociation step since step
they since they are
are more more concentrated
concentrated towards
towards the surface than strongly hydrated cations like
the surface than strongly hydrated cations like Li+ . However, when the pH and, hence, Li +. However, when the pH and,
hence,
the the near-surface
near-surface cation concentrations
cation concentrations are high, arethe
high, the buildup
buildup of these of species
these species
at the at outerthe
outer Helmholtz
Helmholtz plane planeinhibits inhibits
the HER.the This
HER.isThis is particularly
particularly evident evident
on Pt, onwherePt, where
a change a change
in the
in the RDS is shown around pH 13 when employing an
RDS is shown around pH 13 when employing an electrolyte that contains Li or K+ .or K . electrolyte that contains Li
+ + +
Guha et
Guha et al.al. [113,114]
[113,114] conducted
conducted an an extensive
extensive studystudy on on how
how supporting
supporting ions ions like
like Li Li++
can influence
can influence the the HER
HER activities
activities ofof metals.
metals. They They have
have disclosed
disclosed that that highly-concentrated-
highly-concentrated-
electrolyte (sometimes called ‘water-in-salt’-type
electrolyte (sometimes called ‘water-in-salt’-type electrolytes)-based catalysis electrolytes)-based catalysis signifi-
significantly
cantly impacts
impacts the intrinsic
the intrinsic catalyticcatalytic
activity activity
of metals of metals
without without
causing causing
permanentpermanent
surface surface
alter-
alterations. In one of their works, Guha et al. [114] investigated
ations. In one of their works, Guha et al. [114] investigated the impact of the Li ion con- the impact of the
+ Li + ion
concentration
centration on the on HER
the HER of polycrystalline
of polycrystalline Pt and Pt Au.
and TheyAu. They found found that various
that various lithiumlithiumsalts
salts can modify the HER abilities of both materials. Specifically,
can modify the HER abilities of both materials. Specifically, increasing Li concentration increasing + Li + concentra-
tion suppresses
suppresses Pt’s HER Pt’s activity
HER activity while enhancing
while enhancing it in Auit(Table
in Au1).(Table
These1). These
effects wereeffects were
observed
observed
with various with counter-ions such as Li+ , Na
various counter-ions + , ClO
such as4 −Li +, −
, Cl Na +, ClO4−, Cl−, and bis(trifluoro-
, and bis(trifluoromethanesulfonyl)-
imide (TFSI− ) ions and across
methanesulfonyl)-imide (TFSIdifferent
−) ions and across diﬀerent pH conditions (pH 2−13). The
pH conditions (pH 2−13). The effects of the lithium
effectsLiClO
salts, of the 4 , lithium
LiCl, andsalts, LiClO
LiTFSI, on 4 , LiCl,
the HER andprocess
LiTFSI,ofon AuthewereHER process of Au
comparable. were com-
An increase in
parable. An increase in the concentration of LiClO from
the concentration of LiClO4 from 0.01 to 5 M in 0.01 M HClO4 (pH = 2) and 0.1 M NaOH
4 0.01 to 5 M in 0.01 M HClO 4 (pH
= 2) and
(pH = 13)0.1
has Mled NaOH to a (pH
shift=in13)
thehas
HER ledonset
to a shift in the in
potential HERtheonset potential
positive in the
direction, positive
indicating
direction,
the indicating
improvement the improvement
in HER activity. The HER in HER activity.
response shows Thea HER response
comparable shows
effect of Lia+com-ions
parable
on the Au effect of Li+ with
electrode ions on the
LiCl Aulithium
and electrode with LiCl and lithium trifluoromethanesul-
trifluoromethanesulfonate (LiOTf) electrolytes.
Conversely,
fonate (LiOTf) it iselectrolytes.
demonstrated that LiTFSIitsuppressed
Conversely, is demonstrated the HER onLiTFSI
that the Pt electrode,
suppressed while the
LiClO
HER on 4 or LiCl
the Pt does not
electrode, affect
while the
LiClOHER 4 of
or Pt.
LiClMoreover,
does not the
affectHER
the activities
HER of of
Pt. Pt and
Moreover, Au
were found to be unaffected by Na + ions (originating from NaClO +). The authors deduced
the HER activities of Pt and Au were found to be unaffected by Na4 ions (originating from
that
NaClO the4).observed
The authors variations
deduced in that
the HER catalyticvariations
the observed activity are in caused
the HERbycatalytic
changesactivity
in the
adsorption
are caused by energies
changes of various metal ionsenergies
in the adsorption toward Au and Pt metal
of various electrodes.
ions toward Au and Pt
electrodes.
Table 1. Hydrogen concentration and rate of hydrogen formation on Pt and Au electrodes in different
electrolytes. Reprinted from Ref. [114]. Copyright 2018 American Chemical Society.
Applied Potential Duration Hydrogen Concentrationn Rate of Formation

Electrode Electrolyte
(V vs. Ag/AgCl) (mins) (ppm) (×10−8 mol·s−1 ·cm−2 )
Pt 0.1 M LiTFSI −1.1 5 16,550 4056
Pt 20 M LiTFSI −1.1 5 15,799 3872
Au 0.1 M LiClO4 −1.5 5 5755 2635
Au 5 M LiClO4 −1.5 5 7773 3559
Au 0.1 M LiTFSI −1.5 5 7950 3640
Au 20 M LiTFSI −1.5 5 15,577 7132
Additionally, Guha et al. [73] investigated the mechanism behind a tunable HER on
various metals at different pH levels using linear sweep voltammetry (LSV), electrochemical
impedance spectroscopy (EIS), and Tafel analysis. The study investigated Pt, Ir, Pd, Au, Fe,
and Ni catalysts, covering both sides of the Sabatier HER volcano plot, and assessed their
HER efficiency under varying Li+ concentrations. The results revealed that Au, Fe, and Ni
exhibited enhanced HER properties with a higher Li+ concentration, while Pt, Pd, and Ir
showed the opposite trend. Moreover, to study the role of anion and LiF formation, the
authors have evaluated the effect of different Li+ concentrations using both LiCl and LiClO4 .
Similar to the results obtained with LiTFSI, an increase in the Li+ concentration from 1 M to
5 M (in both LiClO4 and LiCl) has led to HER enhancement on the Au, Fe, and Ni electrodes,
while HER suppression was observed on Pt and Ir electrodes. These results offer evidence to
support the authors’ claim that the suppression of the HER in Pt and Ir is not solely caused
by LiF. Figure 5a displays the LSVs for Ir at two different LiTFSI and LiCl concentrations.
The authors observed that the suppression of the HER in Pt and Ir with LiTFSI was more
significant compared to LiCl and LiClO4 . Likewise, for the other metals (Au, Fe, and
Ni), the HER enhancement in LiTFSI was lower than in LiCl and LiClO4 (see Figure 5b),
indicating the potential formation of LiF, as reported by Suo et al. [78]. The authors
confirmed the formation of LiF on the Au, Pt, and Ir electrode surfaces through X-ray
photoelectron spectroscopic (XPS) measurements and using attenuated total reflectance
Fourier-transform infrared spectroscopy (ATR-FTIR) analyses after the electrolysis. The
presence of LiF on the Au electrodes led them to conclude that LiF formation is not the sole
reason for the HER suppression with LiTFSI-based aqueous electrolytes, as was previously
reported [78]. To verify the effect of Li+ (using different LiTFSI concentrations) in shifting
the HUPD desorption peak of Pt, the authors have also conducted various tests using CVs,
LSVs, and EIS in acidic 0.5 M H2 SO4 (pH = 0) and alkaline 0.1 M NaOH (pH = 13). The
CVs of Pt confirm that the HBE of Pt decreased with the increase in the Li+ concentration
in both H2 SO4 and NaOH electrolytes. The variation in metal HBE of the five metals
with varied Li+ concentrations was also verified by the authors theoretically using DFT
and MD studies. Therefore, using theoretical studies, the authors deduced that there is a
variation in the metal HBE with changing the Li+ concentration. At the same time, their
experimental results demonstrated variations in the Pt-H and Pd-H binding energies with
the Li+ concentration. Therefore, this study revealed that metals from both sides of the
volcano plot can exhibit tunable HER properties, regardless of pH levels (0 and 13) and
counter-ions (TFSI− , Cl− , ClO4 − , NO3 − , and OH− ), by modifying the M–H bond energy
using Li+ ions.
Another contribution by Guha et al. [113] investigated the use of high-concentration
Li+ -ion-containing electrolytes for enhancing the electrocatalytic HER performance of
different types of carbon nanotubes (CNTS), namely, metallic multi-wall ones (MWCNTs)
and semiconducting single-wall ones (SWCNTs). The outcomes indicated that both the
CNTs exhibited an enhancement in their HER performance with the increase in Li+ ion
concentration. To validate the mechanism and establish the significance of Li+ in improving
the HER of the CNTs, the researchers also explored several lithium salts with different
counter-ions, such as TFSI− , OTf− , ClO4 − , Cl− , and OH− . Interestingly, they observed a
similar enhancement in the HER characteristics of the CNTs. This study suggested that
anions play a minor role in the observed phenomenon. Although Suo et al. [78] noted that
LiF formation in LiTFSI- and LiOTf-based electrolytes may present a kinetic barrier for
proton reduction, higher concentrations of LiTFSI and LiOTf have actually improved the
HER performance of the CNTs. Additionally, these electrodes exhibited excellent long-
term stability in their HER performance. This study demonstrated that even the slow HER
kinetics of CNTs in an alkaline solution can be improved by using an electrolyte-engineering
strategy without permanently modifying the surface of the catalyst.
(a) (b)
Figure 5. Linear sweep voltammetries of (a) Ir and (b) Au in two different LiClO4 concentrations.
Figure 5. Linear sweep voltammetries of (a) Ir and (b) Au in two different LiClO4 concentrations.
Reproduced from Ref. [73] with permission from the Royal Society of Chemistry.
Reproduced from Ref. [73] with permission from the Royal Society of Chemistry.
Another contribution
Comprehending the HERby Guha et al. [113]
mechanism in investigated
bicarbonate the use of high-concentration
electrolytes is vital for CO2
Li -ion-containing
+
reduction electrolytes
electrocatalysis, for enhancing
considering the electrocatalytic
the widespread occurrence HER performanceinofCO
of bicarbonate dif--
2
ferent types of carbon nanotubes (CNTS), namely, metallic
saturated solutions and the imperative to inhibit HER activity. As already discussed inmulti-wall ones (MWCNTs)
and semiconducting
Section 2.1, Koper et al. single-wall
[99] explored ones the(SWCNTs). The outcomes indicated
HER in bicarbonate-containing that both
electrolytes on Authe
CNTs exhibited an enhancement in their HER performance
and Pt electrodes and observed an increased HER rate with a bicarbonate buffer. Despite with the increase in Li+ ion
concentration.
the rise in surface To validate
pH fromthe mechanism
water reduction and
(2H establish the significance−of Li+ in improv-
−
2 O + 2e → H2 + 2OH ), bicarbonate is
ing the HER
consumed of the CNTs,
through acid–basethe researchers
reactions and alsothe explored several
bicarbonate lithium
branch of salts with becomes
the HER different
counter-ions,
prominent only such
withassubstantial
TFSI−, OTfbulk−, ClO4−, Cl−, and OH−. Interestingly, they observed a sim-
buffer concentrations. Based on this study, the authors
ilar enhancement
deduced in the HER
that bicarbonate and characteristics
water reduction of the CNTs.
seem This study suggested
fundamentally that anions
distinct, displaying
play a minor role in the observed phenomenon. Although Suo
contrasting reliance on the cation identity and scaling differently with the electrode’s et al. [78] noted that LiF
formation in LiTFSI- and LiOTf-based electrolytes may present
specific area. Using microkinetic modeling, the researchers ruled out the explanation a kinetic barrier for proton of
reduction,
the HER inhigher concentrations
bicarbonate of LiTFSI
through proton and LiOTf
generation have actually
in acid–base improved
reactions. the HER
Instead, they
performance
proposed of the
a direct CNTs. Additionally,
bicarbonate these electrodes
reduction pathway, emphasizing exhibited excellent
its strong long-term
dependence on
stability
the cationinconcentration
their HER performance. This studycharged
due to the negatively demonstrated
reactant. that even the slow HER ki-
netics of CNTs
Koper et al.in[115]
an alkaline
studiedsolution
the CO2can be improved
reduction reactionby(CO
using2 RR)anonelectrolyte-engineer-
Au electrodes and
ing strategy
showed that,without
without permanently
a metal cation,modifying the surface
the reaction does ofnotthetake
catalyst.
place in a pure 1 mM
H2 SOComprehending
4 electrolyte. Moreover, the HER utilizing
mechanism scanning electrochemical
in bicarbonate microscopy
electrolytes to for
is vital studyCOCO 2 re-
2
reduction and comparingconsidering
duction electrocatalysis, scenarios with the and without occurrence
widespread metal cations, they found that
of bicarbonate in CO CO 2-
is exclusively
saturated generated
solutions and theon the Au, Ag, to
imperative or inhibit
Cu electrodes when aAs
HER activity. metal cation
already is present
discussed in
in the electrolyte.
Section 2.1, KoperThroughet al. [99]DFT simulations,
explored the HER theinauthors presented conclusive
bicarbonate-containing evidence
electrolytes on
that
Au andpositively charged
Pt electrodes and species fromanthe
observed electrolyte
increased HER play
rateawith
crucial role in stabilizing
a bicarbonate buffer. De-the
spite the rise in surface pH from water reduction (2H2O + 2e → H2 + 2OH ), bicarbonate
key reaction intermediate. In another contribution, Koper et al.
− [116] utilized − rotating ring
disc electrodethrough
is consumed (RRDE)acid–base
voltammetry to assess
reactions and how bicarbonatebranch
the bicarbonate and cation
of theconcentrations
HER becomes
influence CO
prominent only RR and HER currents on an Au disk, impacting
2 with substantial bulk buffer concentrations. Based on this study, the Faradaic efficiency
the au- to
thors deduced that bicarbonate and water reduction seem fundamentally distinct, dis-
playing contrasting reliance on the cation identity and scaling differently with the elec-
trode’s specific area. Using microkinetic modeling, the researchers ruled out the explana-
tion of the HER in bicarbonate through proton generation in acid–base reactions. Instead,
CO (FE(CO)). By varying the bicarbonate and cation concentrations and adjusting rotation
rates, the authors uncovered two distinct potential regimes for electrolyte effects. These
regimes were characterized by an opposite interplay of CO2 RR and the HER kinetics. In
the first regime (low negative potential), higher HCO3 − and Na+ concentrations enhance
FE(CO). Conversely, in the second regime (more negative potential), lower HCO3 − and
Na+ concentrations are preferred to suppress the HER. This study provides in-depth
insights into the impact of electrolyte composition and mass transport, aiding in defining
the optimized electrolyte conditions for achieving a high FE(CO). Interested readers are
recommended to explore a brief review on the effects of electrolytes on CO2 RR by Koper
et al. [117]. The review highlights the crucial role of cations in co-ordinating and stabilizing
the initial electron transfer intermediate, CO2 − , in the CO2 reduction to CO. The kinetics
of the reaction are significantly influenced by the cation’s characteristics, including the
hydration number and acidity. For optimal performance, the study suggests using weakly
hydrated alkali cations like Cs+ or K+ to achieve a high current density regardless of the pH,
while intermediate cation concentrations (≤0.1 M) are preferred due to their promotion of
concomitant water and bicarbonate reduction. In a more recent study, Koper’s group [118]
explored the impact of cations on HCOOH and CO formation during CO2 RR on PdML Pt-
(111) in pH 3 electrolytes. The absence of metal cations resulted in the formation of only a
small amount of adsorbed CO, while increasing cation concentrations led to a decrease in
the onset potential of HCOOH and CO. Using DFT simulations, the study uncovered that
the formation pathways of both CO and HCOOH involve negatively charged intermediates,
such as negatively charged adsorbed CO2 and adsorbed hydride, whose formation is
enhanced by interactions with cations.
In the context of electrolyte and cation effects on electrocatalysis, it is important to
mention the study of Strmcnik et al. [106], who explored how Li+ , Ba2+ , and K+ impact
Pt and Au during the ORR in an alkaline solution. They observed that, in an alkaline
environment, Li+ had a strong interaction with adsorbed OH− ions at the active sites of the
Pt surface, leading to the blocking of these active sites for the ORR on Pt. Therefore, the
presence of Li+ results in a decrease in the ORR activity of the Pt surface. However, this
effect was not observed on the Au surface due to the small coverage of OH− ions on the
Au surface. A DFT study conducted by Matanović et al. [119] provides additional evidence,
indicating that, when H+ ions are present at low concentrations, alkali metal ions compete
with them for adsorption on the Pt surface, blocking the active sites on the Pt surface and
suppressing the HER. As the Li+ concentration rises, the H+ concentration falls relative to
the Li+ concentration, creating strong competition between Li+ and H+ for adsorption on
the Pt surface [78]. The effect of alkali metal cations (originating from MClO4 , where M
refers to Li+ , Na+ , K+ , Rb+ , or Cs+ ) on the electric double layer (EDL) capacitance of Pt(111)
and Au(111) electrodes was investigated by Garlyyev et al. [120]. The study revealed that
the local effective concentrations of cations near the electrode for both Pt(111) and Au(111)
electrodes can reach ~80 times higher than those in the bulk solution. The EDL capacitance
increased linearly Li+ < Na+ < K+ < Rb+ < Cs+ , indicating a significantly higher effective Li+
concentration within the double layer compared to the bulk solution. Another DFT-based
theoretical work [121] revealed that Pt has a greater affinity to Li+ ions compared to Au.
According to the DFT calculations, the adsorption potential of Li+ on the surfaces of Pt and
Au is −1.30 V and −2.76 V vs. NHE, respectively. As a result, the strongly adsorbed Li+
ions block the active sites of Pt, hindering the HER. Additionally, Li+ has the capacity to
destabilize water molecules [46], and the high Li+ concentration near the electrode surface
may be favoring the breakdown of water molecules, which would then result in increased
the HER activity of Au where the surface is not obstructed by Li+ ions.
In our recent work [55], we have investigated the effect of the nature of the electrolyte
(0.1 M HClO4 , 0.1 M HCl, 0.5 M NaCl, 1 M KH2 PO4 , 0.1 M KOH, 1 M KOH, and 0.1 M
LiOH) on the HER activity of various monometallic polycrystalline electrodes (Pt, Ni, W,
Co, Fe, Cr, Ag, Au, and Zn), both for freshly polished and oxidatively treated electrodes.
In order to compare the HER catalytic activities of the investigated metals in the various
electrolytes, we have determined the overpotential values required to achieve a current

density of −0.1 mA cm−2 real (η 0.1,real ). The HER activity of the metals in the investigated
electrolyte solutions, as determined by the η 0.1,real , follows the following order: 0.1 M
HClO4 > 0.1 M LiOH > 1 M KH2 PO4 > 0.1 M HCl > 1 M KOH > 0.1M KOH > 0.5 M NaCl.
The HER of the metals in LiOH was remarkably high, which is attributed to the effect of
the Li ions [111,122]. The higher HER activity of metals in a 1 M KH2 PO4 solution can be
attributed to the effect of K+ ions, the buffering properties of KH2 PO4 , and the involvement
of weak acid components (H2 PO4 − and HPO4 2− ) in the reduction process, as suggested by
previous studies [71,94,100]. It is widely accepted that the accelerated formation of Hads
intermediates from H3 O+ significantly enhances the HER activity of metals in the acidic
solutions (0.1 M HClO4 and 0.1 M HCl). While the higher activity of the metals in 0.1 M
HClO4 can be ascribed to the non-adsorbing property of the ClO4 − anion [75], conversely,
the decreased activity of the metals in the HCl and NaCl solutions can be attributed to the
negative effects of Cl− ion poisoning. The higher HER activity of the metals in 1 M KOH
compared to 0.1 M KOH is primarily due to the concentration effect of K+ ions [123].
There are conflicting views on the influence of electrolyte anions on the HER. Some
studies suggest their effect is insignificant, as already exemplified, while others reveal
that electrolytes can significantly influence the HER of metal catalysts. A comparable
HER/HOR performance of Pt across three electrolytes (HClO4 , HNO3 , and H2 SO4 ) is
reported in Ref. [124]. Moreover, Ref. [125] shows that, in contrast to the HOR, the HER
current densities, which have been examined in low overpotential and underpotential
sites, were found to be independent of the nature of the supporting electrolyte (HClO4 ,
H2 SO4 , and HCl). Similar HOR/HER activities in the presence of H2 SO4 − and HClO4 −
ions were reported, which could be possibly because these counter-anions may not adsorb
on the catalyst surface at HOR/HER-relevant potentials in the vicinity of ≈ 0 VRHE [80].
Moreover, as already discussed, Guha et al. [113] revealed that the effect of the nature of
anions (TFSI− , OTf− , ClO4 − , Cl− , and OH− ) on the HER of the CNTs was minor.
Several studies have explored how strong anion adsorption on PGM surfaces influ-
ences the kinetics of pseudo-capacitive and Faradic processes. Anions can also adsorb on
the electrode surface at potentials below the potential of zero charge, particularly within
the HUPD region, impacting Pt-Had energetics and potentially causing alterations in the
HER kinetics [80]. In practical terms, anionic contamination from SO3 − ions, which may
be released during polymer electrolyte membrane degradation in electrolyzer/fuel cell
operation, could adversely affect device performance and durability, especially with ultra-
low PGM loadings. Furthermore, the presence of Br– and I– were reported to significantly
reduce the overall rates of the HER/HOR [80].
As already mentioned, our recent study [55] revealed the effect of both cations and
anions on the HER of different metals. More specifically, the impact of Cl− ions was
significant in both 0.1 M HCl and 0.5 M NaCl. This effect was evident on the volcano plots
(a plot of the HER overpotential values needed for the current density of 0.1 mA cm−2 real ,
vs. the DFT-calculated HBE) (Figures 6 and 7). One can easily observe the impact of the
electrolyte on the shape of the volcano curve, as evidenced by the broader overpotential
range (from ~0 to >−0.6 V) required for the HER in HCl (Figure 6b) compared to HClO4
(Figure 6a), which can be attributed to the Cl− ion poisoning in 0.1 M HCl and the non-
adsorbing property of the ClO4 – anion in 0.1 M HClO4 . The effect of electrolytes is also
noticeable in neutral solutions, with NaCl (Figure 7a) exhibiting higher HER overpotentials
than KH2 PO4 (Figure 7b). Moreover, the volcano peak shifts by approximately −0.3 V,
and unique characteristics such as flattened trends for W and Cr are observed in the NaCl
solution. At the same time, Co exhibits unexpectedly low activities in both the pH-neutral
solutions investigated. These findings align with the concepts proposed in Ref. [126], which
discuss the activity of metals with highly exothermic hydrogen adsorption. The effect of
SO4 2− and ClO4 − anions on the HER activity of Pt(110) in 0.1 M KOH was examined by
Sheng et al. [75]. ClO4 – was shown not to affect the HBE, while the addition of SO4 2−
slightly altered the HBE of Pt(110).
unique characteristics
unique characteristics suchsuch as
as flattened
flattened trends
trends for
for WW and
and Cr
Cr are
are observed
observed in
in the
the NaCl
NaCl
solution. At the same time, Co exhibits unexpectedly low activities in both the
solution. At the same time, Co exhibits unexpectedly low activities in both the pH-neutral pH-neutral
solutions investigated.
solutions investigated. TheseThese findings
findings align
align with
with the
the concepts
concepts proposed
proposed in in Ref.
Ref. [126],
[126],
which discuss
which discuss the the activity
activity of
of metals
metals with
with highly
highly exothermic
exothermic hydrogen
hydrogen adsorption.
adsorption. The
The
effect of SO 2− and ClO4− anions on the HER activity of Pt(110) in 0.1 M KOH was examined
42− −
effect of SO4 and ClO4 anions on the HER activity of Pt(110) in 0.1 M KOH was examined
Hydrogen 2023, 4 by Sheng
by Sheng etet al.
al. [75]. ClO44── was
[75]. ClO was shown
shown not
not to
to affect
affect the
the HBE,
HBE, while
while the
the addition
addition of SO793
of SO 42−
42−
slightly altered
slightly altered thethe HBE
HBE ofof Pt(110).
Pt(110).
(a)
(a) (b)
(b)
Figure 6.
6. The HER
TheHER volcanoes
HERvolcanoes ininacidic
volcanoesin solutions:
acidicsolutions: (a)(a)
solutions:(a) 0.1 MM HClO 4; and (b) 0.1 M HCl. Freshly pol-
Figure The acidic 0.10.1
M HClOHClO 4 ; and
4; and (b) (b) 0.1HCl.
0.1 M M HCl. Freshly
Freshly pol-
ished electrodes are represented by squares, and circles are used to represent electrodes after un-
ished electrodes
polished are are
electrodes represented
representedby squares, andand
by squares, circles are are
circles usedused
to represent electrodes
to represent afterafter
electrodes un-
dergoing oxidative treatment. Reproduced from Ref [55]. This work is an open-access article distrib-
dergoing oxidative
undergoing treatment.
oxidative Reproduced
treatment. Reproducedfromfrom
Ref [55].
Ref This
[55].work
This iswork
an open-access article distrib-
is an open-access article
uted under the terms and conditions of the Creative Commons Attribution (CC BY).
uted under under
distributed the terms
the and
termsconditions of the Creative
and conditions Commons
of the Creative Attribution
Commons (CC BY).
Attribution (CC BY).
(a)
(a) (b)
(b)
Figure 7. The HER volcanoes in neutral solutions: (a) 0.5 M NaCl (simulated sea water); and (b) 1 M
KH2 PO4 (pH was adjusted to 7.0 in both electrolytes). Freshly polished electrodes are represented by
squares, and circles are used to represent electrodes after undergoing oxidative treatment. Regarding
the NaCl solution, significant changes in activity are indicated by arrows. Reproduced from [55]. This
work is an open-access article distributed under the terms and conditions of the Creative Commons
Attribution (CC BY).
Seawater electrolysis, a key process for green hydrogen production, encounters many
challenges, including the concentration overpotential and iR drop [3]. Aiming to enhance
the efficiency of seawater electrolysis, a recent study by [127] introduced a novel mixed
buffer electrolyte with a 1:1 borate/carbonate molar ratio with a new apparent pKa (pKa,app )
of pH 9.8. The electrolyte deliberately incorporates concentrated Cl− , achieving a conductiv-
ity of about 50 S m−1 at 353 K, which is on par with 30 wt % KOH (~130 S m−1 ). The mixed
buffer electrolyte with Cl− optimizes the hydrogen and oxygen evolution reactions using
RuNiOx Hy /Ni felt and CoFeOx Hy /Ti felt, respectively. Through electrolyte engineering,
cation concentration tuning, and pH adjustment, a zero-gap cell was achieved, operating
stably at 2.00 V and 500 mA cm−2 for 80 h with minimal iR loss. This design showcases an
innovative approach to seawater splitting for enhanced electrolytic performance.
2.3. Electrolyte Concentration and HER Kinetics

Arminio-Ravelo et al. [128] studied the effect of electrolyte composition and concentra-
tion on commercial Ir black nanoparticles using varying concentrations (0.05 M, 0.1 M, and
0.5 M) of H2 SO4 and HClO4 . It was found that H2 SO4 hindered Ir oxidation and catalyst
performance, while HClO4 showed minimal interference and a better catalytic performance
than H2 SO4 , regardless of its concentration. Varying concentrations of HClO4 showed no
significant impact while an increasing H2 SO4 concentration led to decreased activity due
to the stronger adsorption of HSO4 − and SO4 2− anions on the catalyst surface compared to
ClO4 − anions. HClO4 is suitable for catalytic performance as it has minimal impact, but
concentrations higher than 0.1 M should be avoided to prevent potential anion interactions.
The authors recommend using HClO4 as the electrolyte for benchmarking and reporting
activity and stability trends in the RDE measurements of Ir-based materials.
The effect of the nature of the electrode (polycrystalline and nanostructured), pH
(12 to 14), and concentration of the electrolyte (0.01 to 2 M KOH) on the HER activity of
Ni-based catalysts was investigated by Faid et al. [129]. The findings showed that a pH
and KOH concentration variation influenced the HER activity by affecting the ECSA and
Tafel slope. The nanostructured NiMo catalyst exhibited an enhanced HER activity, and
the Tafel slope was reduced from ~−180 mV dec−1 to −60 mV dec−1 in the pH range of
12–14 and KOH concentrations of 0.01–1.0 M, indicating a promoting region for both the
ECSA and reaction order. Polycrystalline Ni showed different behaviors in different pH
and KOH concentration regions, maintaining Tafel slopes around −120 mV dec−1 . How-
ever, both catalysts’ HER performances were inhibited under the conditions of decreased
OHad transport kinetics. The higher HER activity of various metals in 1 M KOH than in
0.1 M KOH was also observed in our recent work [55]. Moreover, Li et al. [130] observed
that the HER activity of Pt(pc) was improved with the increase in NaOH concentration
from 0.01 M (pH 12) to 1.0 M (pH 14). Kuznetsov et al. [131] observed that the anodic
charge and ECSA of NiCu/C catalysts were influenced by the NaOH concentration. They
also found that the HER activity of a partially oxidized Ni disc electrode improved with
increasing pH/NaOH concentrations when the potential was below −0.18 V vs. RHE.
Moreover, current densities in cyclic voltammograms were found to vary with changes in
the electrolyte concentration, resulting in variations in the apparent ECSA of Ni nanostruc-
tures [132]. Goyal et al. [123] investigated the impact of the electrolyte pH and alkali metal
cation concentration on the HER kinetics on Au electrodes. They found that increasing the
cation concentration significantly enhances the HER activity at a moderately alkaline pH
(pH = 11) by accelerating the sluggish Volmer step. It is highlighted that the electrolyte
pH and bulk cation concentration affect the surface cation concentration and influence the
water dissociation kinetics, with interfacial cations stabilizing the transition states. Yet,
excess near-surface cations, particularly at elevated pH and cation levels, can impede HER
activity by obstructing active sites.
Furthermore, studies indicate that optimizing the electrolyte composition can signifi-
cantly enhance mass transport and improve the efficiency of the HER, particularly when
operating at near-neutral pH conditions [92,133]. Shinagawa et al. [94] studied, both exper-
imentally and theoretically, the effect of the electrolyte concentration on the Pt electrode
under neutral-buffered conditions, employing sodium phosphate (0.2–4.2 M at pH 5) as the
electrolyte solution. Both experimental and theoretical research revealed a volcano-shaped

relationship between the solute concentration and HER activity. The HER performance
increased with solute concentrations up to 2 M, but higher concentrations resulted in
decreased performance. Their microkinetic model combined with a description of mass
transport closely matched the experimental results, indicating the presence of notable
concentration overpotentials during the HER under buffered-neutral conditions. Their sim-
ulation model indicated that the concentration overpotential surpassed 46% even at 0.5 M,
while the kinetic overpotential remains the lowest (~10%) due to sluggish mass transport.
The authors emphasized that mass transport is influenced by diffusion and activity coeffi-
cients, with the former determined by ion size and electrolyte viscosity. Thus, adjusting
these parameters through effective electrolyte engineering can significantly enhance HER
performance in neutral conditions, regardless of the electrocatalyst used.
During water splitting, oxygen is evolved at the anode (OER) and can migrate to
the cathode, where catalysts for the HER also facilitate the oxygen reduction reaction
(ORR). Oxygen crossover between the anode and cathode in membraneless cells reduces
the HER efficiency due to undesired competitive reactions, underscoring the need for an
oxygen-tolerant HER to improve efficiency. Shinagawa et al. [92] found that selecting the
proper electrolyte enhances cell efficiency by controlling the mass transport of oxygen and
the proton source (for example, weak acid). The study extensively analyzed the influence
of different solutes on the HER and ORR under heavily-buffered conditions. They tested
various electrolyte solutions, including KH2 PO4 , K2 HPO4 , K3 PO4 , LiH2 PO4 , NaH2 PO4 ,
NaHCO3 , HClO4 , and KOH, and mixtures of them, in the concentration range of 0.01 to
3.0 M. Under specific conditions (1.5 M NaH2 PO4 or 1.5 M 40% K2 HPO4 + 60% KH2 PO4 ),
the overpotential required to achieve −10 mA cm−2 was found to be less than −40 mV with
a 90% selectivity towards the HER in oxygen-saturated electrocatalytic conditions (Figure 8).
Using such highly concentrated buffers also reduced solution resistance, further enhancing
the overall HER performance. The existing literature highlights that the concentration of
electrolytes plays a crucial role in the electrocatalytic HER, having a positive impact up to a
certain threshold level, beyond which it adversely affects the HER.
2.4. Effect of Electrolyte Impurities

Electrolyte impurities can substantially impact the HER kinetics, causing the reduced
efficiency or complete inhibition of the reaction. Common impurities found in the elec-
trolyte are metal ions, organic contaminants, and other foreign substances, which can
modify the electrode’s surface properties, affect the reaction kinetics, and cause undesired
side reactions during the HER. Impurities in electrolysis cells can originate from various
sources. For instance, commercial KOH electrolytes may contain Zn as an impurity [6],
while Pt and Au counter-electrodes used in measurements can also introduce contami-
nants [80]. Moreover, impurities can arise from corrosion products of cell components
due to the corrosive environment caused by highly alkaline electrolytes, high temperature,
and the presence of molecular oxygen [134]. The HER activity of surfaces with low j0
values can be influenced by trace metal cations in the electrolyte, which can plate onto the
surface due to the HER starting at low potentials [80]. Impurities can deposit as metallic
species during H2 production through cathodic reduction or as salts/hydroxides through
chemical precipitation, causing the passivation of catalytically active sites [134]. Weber
et al. [135] investigated the challenges in benchmarking the HER/HOR activity of Pt-based
catalysts in alkaline media, viz., 0.1 M LiOH, NaOH, and KOH. They analyzed the elec-
trochemical setup (such as the cell material, hydrogen gas, and electrolyte solutions) to
identify the source of the impurities. They identified glass cells and hydrogen gas as
non-significant sources of contamination. However, they noticed a significant reduction in
the ECSA of Pt following HER/HOR measurements, especially in 0.1 M NaOH and LiOH
solutions. Through long-term chronoamperometric experiments and X-ray photoelectron
spectroscopy analysis, the authors discovered that trace metals (Cu, Zn, Pb, and Fe) from
electrolyte salts were deposited on the Pt surface during the HER.
Hydrogen 2023,4 4, FOR PEER REVIEW
Hydrogen2023, 79621
Figure8.8.Calculated
Figure CalculatedFaradaic
Faradaicefficiency
efficiencyto
tothe
theHER
HERininvarious
variouselectrolyte
electrolytesolutions
solutions using
using aapoly-
poly-
crystalline Pt disk electrode.Reprinted with permission from Ref. [92]. Copyright (2016) American
crystalline Pt disk electrode.Reprinted with permission from Ref. [92]. Copyright (2016) American
Chemical Society.
Chemical Society.
2.4. Studies
Effect of Electrolyte
show thatImpurities
the presence of trace metal cations can have both positive and
negative Electrolyte
effects on impurities
the HERcan substantially
activity impact themetal
of the substrate HER kinetics,
[80]. Li etcausing thestudied
al. [136] reduced
the influence
efficiency or of trace iron
complete impurities
inhibition and
of the alkali metal
reaction. Common cations (Na+ and
impurities Cs+ )inonthe
found theelectro-
HER
oflyte
polycrystalline
are metal ions,Cu electrodes
organic in alkaline
contaminants, andconditions.
other foreign The study found
substances, which that,
canduring
modify
electrolysis in 0.1surface
the electrode’s M solutions of NaOH
properties, andthe
affect CsOH, with kinetics,
reaction the highestand commercially
cause undesired available
side
purity grades, small amounts of iron impurities were deposited
reactions during the HER. Impurities in electrolysis cells can originate from various on the Cu electrode. The
presence
sources. of Foriron impurities
instance, significantly
commercial KOH accelerated
electrolytesthe may HER rate in
contain Zn0.1as M
anCsOH
impurityby up
[6],
towhile
five times
Pt andover
Au eleven CVs. The authors
counter-electrodes used have pre-electrolyzed
in measurements the electrolyte
can also introduce solution
contami-
tonants
remove[80].iron impurities
Moreover, effectively,
impurities and,from
can arise aftercorrosion
removing the ironofimpurities,
products cell components the CVs
due
stabilized with the cycle number. For purified electrolytes (0.1
to the corrosive environment caused by highly alkaline electrolytes, high temperature, M NaOH and CsOH),
the
andHER current densities
the presence of molecularwereoxygen
found [134].
to be The
nearlyHER identical,
activity suggesting no significant
of surfaces with low j0 val-
cation effect on the HER rate on Cu. Similar findings are reported for
ues can be influenced by trace metal cations in the electrolyte, which can plate onto the other electrocatalytic
reactions,
surface due liketothe
theOER.
HERKlaus et al.
starting at [137] studied the
low potentials influence
[80]. of Fecan
Impurities incorporation on the
deposit as metallic
structure–activity
species during Hrelationships in Ni-(oxy)hydroxide by analyzing aged Ni(OH)2 /NiOOH
2 production through cathodic reduction or as salts/hydroxides through
films
chemical precipitation, causing the passivation of catalytically active sites [134]. Weberinet
in KOH using various characterization techniques. They discovered that aging
unpurified KOH led to
al. [135] investigated thea challenges
>20% Fe incorporation
in benchmarking after the
fiveHER/HOR
weeks, resulting
activityin ofaPt-based
higher
OER activity, lower overpotential, and lower Tafel slope compared
catalysts in alkaline media, viz., 0.1 M LiOH, NaOH, and KOH. They analyzed the elec- to samples aged in
Fe-free KOH. Optimal catalyst activity was observed with five-day
trochemical setup (such as the cell material, hydrogen gas, and electrolyte solutions) to aging in unpurified 1
M KOH. Salmanion et al. [138] explored the OER of Co and Au in Ni-
identify the source of the impurities. They identified glass cells and hydrogen gas as non- and Fe-free KOH.
The results demonstrated that cobalt oxide served as a relatively efficient catalyst for the
OER in a pure electrolyte, while gold does not exhibit good catalytic activity under the
same conditions. Iron impurities in the form of FeO2 – present in commercial 1.0 M KOH
electrolytes are actually known to react with Au electrode surfaces and create active sites for
the OER [139]. Moreover, Gong et al. [140] reported that Fe had a synergistic effect with Co,
Ni, Cu, Ag, and Au (but not Ti) in enhancing the OER. Although the Co electrode showed
good OER catalytic activity in a pure electrolyte, its Tafel slope decreased significantly in the
presence of Ni-containing (Fe-free) KOH [138]. The study suggests that Ni ions precipitate
on the electrode’s surface, altering the redox-active sites, emphasizing the significance of
trace electrolyte impurities and proposing the use of pure electrolytes for evaluating the
electrocatalysts’ performance for the OER. Extensive research has explored how arsenic
compounds affect the HER and HUPD on Pt, Ni, and steel electrodes. Even trace amounts
of arsenic (~10−8 M) were consistently found to reduce j0 and increase he overpotential for
the HER [141–143].
Moreover, both PEMEL and AEL cells can have two types of impurities: exogenous
and endogenous. Electrolyzers usually need highly purified water, but the purified water
may still contain low concentrations of ionic species and total organic carbon, considered
as exogenous impurities [144]. The growing adoption of green hydrogen technology may
raise the pure water demand, thus creating public concerns in water-scarce areas. Re-using
purified wastewater could address this, but it is energy-intensive and expensive. Opting
out of proper purification for industrial processes risks contaminating electrocatalysts with
impurities from untreated water [1]. Endogenous impurities in electrolyzer systems, on the
other hand, originate from internal sources. Throughout its operation, electrolyzers may
undergo a gradual deterioration of their stack and balance of plant (BoP) parts, resulting in
the production of impurities within the system. Additionally, impurities may arise from
component leaching and contamination during the electrolyzer manufacturing, commis-
sioning, and maintenance processes. Cations in PEMWEs present significant challenges
as impurities, impacting the catalyst, ionomer, and membrane. Their presence can lead to
performance degradation and a reduced lifespan, as depicted in Figure 9. Anions are often
associated with initiating side reactions, such as chlorine evolution, potentially affecting
the hydrogen quality and accelerating corrosion in metallic components [144]. In contrast
to cations, anions cannot replace protons within the membrane and ionomer, leading to
different operational mechanisms (Figure 5).
Therefore, to achieve the best HER performance, it is crucial to use high-purity elec-
trolytes and meticulously control their quality to minimize the influence of impurities.
Studies revealed that shielding the counter-electrode and pre-treating the electrolyte can
help minimize the impact of metal cation impurities on the HER. Moreover, an electro-
chemical purification step aimed at diminishing impurities originating from the electrolyte
solution was devised by Weber et al. [135], which demonstrated that pre-electrolyzing the
electrolyte solutions was found to be effective in removing iron impurities. The use of
self-assembling and self-healing catalytically active films to overcome the cathode deac-
tivation triggered by electrolyte impurities is also mentioned in Ref. [134]. According to
this study, introducing a trace metal impurity (Zn) has raised the cell voltage. At the same
time, adding an active material (Nix B) formed a self-assembled catalyst film, restoring
activity and lowering the voltage. To mitigate catalyst poisoning, using more resistant
catalysts is an option. Metal-oxide-based catalysts are less susceptible to poisoning com-
pared to unmodified ones. Catalysts with carbonate, sulfate, and oxide compounds also
display enhanced resilience against deactivation. For instance, the MoS2 electrocatalyst
was found to be more tolerant to sulfur poisoning than Pt/C [1]. Carbon-based materials
like nanotubes or graphene can also mitigate contaminant effects by serving as active HER
electrodes. Despite lacking inherent strong catalytic properties, these materials can be
modified with small catalyst amounts for highly efficient electrocatalysis. Doping graphene
with heteroelements like nitrogen, sulfur, phosphorus, or boron enhances its electrocatalytic
affecting the hydrogen quality and accelerating corrosion in metallic components [144]. In
performance.
contrast Modified
to cations, electrodes
anions cannotalso display
replace a remarkable
protons within resistance to surface
the membrane andpoisoning;
ionomer,
intriguingly,
leading impurities
to different might improve
operational their catalytic
mechanisms capabilities [145–147].
(Figure 5).
Figure 9. Diagrammatic representation of the impact of different types of impurities on PEMWEs.

Figure 9. Diagrammatic representation of the impact of different types of impurities on PEMWEs.
Reproduced from Ref. [144]. with permission from the Royal Society of Chemistry.
Reproduced from Ref. [144]. with permission from the Royal Society of Chemistry.
Therefore,
Besides PEMEL to achieve the bestother
technology, HER important
performance, waterit iselectrolysis
crucial to use high-purity
approaches areelec-
also
trolytes and meticulously control their quality to minimize
impacted by the properties of the electrolyte. These include the standard alkaline water the influence of impurities.
Studies revealed
electrolyzer (AWE), thatanion
shielding the counter-electrode
exchange membrane electrolyzer and pre-treating
(AEME), solid the electrolyte can
oxide electrol-
help minimize the impact of metal cation impurities on the
ysis cell (SOEC), and protonic ceramic electrolysis cell (PCEC) approaches [11]. AWE is HER. Moreover, an electro-
chemical
absolutelypurification
the most mature step aimed
among atthem,
diminishing
typically impurities
employing originating
5–7 mol dm from
−3 KOHthe electro-
as the
lyte solution was devised by Weber et al. [135], which demonstrated
solution. On the other hand, AEME is rapidly developing and has several advantages that pre-electrolyzing
the
overelectrolyte solutions
classical AWE, likewashigherfound to bedensities
current effective in andremoving
a higheriron purityimpurities.
of produced The use of
gases.
self-assembling
Considering AWE andandself-healing
AEME, the catalytically
impact ofactive films to overcome
the electrolyte composition the cathode deacti-
and impurities
vation
can be triggered
regarded by fromelectrolyte impurities
the fundamental is alsofocusing
aspect, mentioned on in
theRef. [134].interactions
specific According to atthis
the
study, introducing a trace metal impurity
electrode interface, as discussed earlier. For example, one of (Zn) has raised the cell voltage. At
advantages of AEME over the same
time,
AWE adding
is higheranvoltage
active material
efficiency(Ni xB) formed
which a self-assembled
is partially due to the mildercatalyst film, environment
alkaline restoring ac-
tivity
(1 moland − 3
dmlowering
KOH).the voltage. the
However, To mitigate
electrolytes catalyst
also poisoning, using more
affect the overall resistant of
performance cata-
an
lysts is an option.
electrolyzer system Metal-oxide-based
through their conductivity catalysts are less susceptible
(causing Ohmic losses), to poisoning
viscosity,compared
solubility
to
of unmodified
gases, and other,ones.moreCatalysts with carbonate,
technical, aspects. sulfate, and oxide compounds also display
enhanced resilience against deactivation. For instance, the MoS2 electrocatalyst was found
3. Summary
to and Outlook
be more tolerant to sulfur poisoning than Pt/C [1]. Carbon-based materials like nano-
tubesThisor graphene can also
review explores themitigate
impact of contaminant
electrolyteseffects by serving
on hydrogen as active
evolution HER(HER)
reaction elec-
kinetics,Despite
trodes. emphasizing
lackingthe pH, cations,
inherent strong anions,
catalyticand impurities.
properties, theseIt materials
briefly covers
can be how the
modi-
electrolyte
fied concentration
with small catalyst affects
amounts HER forkinetics,
highly highlighting its beneficial Doping
efficient electrocatalysis. impact up to a cer-
graphene
tain level,
with beyond which
heteroelements like it hamperssulfur,
nitrogen, efficiency. The electrolyte
phosphorus, or boron pHenhances
significantly influences
its electrocata-
the HER
lytic by alteringModified
performance. the catalyst–electrolyte
electrodes also chemistry and proton resistance
display a remarkable concentrations, affecting
to surface poi-
metal’s hydrogen binding energy, proton donor, water adsorption,
soning; intriguingly, impurities might improve their catalytic capabilities [145–147]. and interfacial water
reorganization.
Besides PEMEL Thesetechnology,
factors collectively determinewater
other important the reaction kinetics,
electrolysis catalyst effective-
approaches are also
ness, and overall
impacted HER efficiency.
by the properties of theAlthough
electrolyte. there are differing
These include the opinions,
standard there is a general
alkaline water
consensus that
electrolyzer (AWE),the HER
anionactivity
exchange tends to decrease
membrane with higher
electrolyzer pH levels.
(AEME), Yet, the
solid oxide HER
electrol-
behavior
ysis in neutral
cell (SOEC), solutions
and protonic presents
ceramic a unique phenomenon.
electrolysis cell (PCEC) Conversely,
approaches neutral
[11].solutions
AWE is
allow for applications
absolutely the most mature such as seawater
among them, utilization
typicallyand eliminate
employing 5–7 the need
mol dmfor specialized
−3 KOH as the
materials or acid/alkali-resistant catalysts. The pH-neutral
solution. On the other hand, AEME is rapidly developing and has several advantages HER is affected by reactant
over
properties, electrolyte state (buffered/unbuffered), and concentrations. The insufficient
H3 O+ ions restrict the HER activity in pH-neutral solutions at the electrode–electrolyte

interface, but buffering enhances the H3 O+ supply. Additionally, studies suggest weak
acids like phosphate species (H2 PO4 − and HPO4 2− ) likely act as reactants under buffered
conditions. In water splitting, oxygen evolved at the anode (OER) can cross to the cathode
in membraneless cells, affecting the HER. For this purpose, heavily buffered electrolytes
are found to exhibit better HER performance with very high selectivity towards the HER in
oxygen-saturated electrocatalytic conditions regulating the oxygen transport and proton
source (for example, weak acid).
Beyond the electrolyte pH, electrolyte ions are also known to impact the kinetics
of the HER. Spectator ions can influence HER kinetics by co-adsorbing or interacting
with adsorbed intermediates on catalyst surfaces. Recent studies show that aqueous
electrolytes with Li+ can effectively enhance various electrochemical reactions, including
the HER. Notably, a ~4-times HER performance difference is observed between Li+ - and
Cs+ -containing electrolytes. Electrolytes with larger (more structure-breaking) cations
exhibit more surface-bound cations than smaller (more structure-making) ones, influencing
the interfacial hydrogen-bonding network and solvent reorganization energy. Larger
cations like Cs+ remove water molecules at the interface through a strong ion–surface
interaction, while smaller cations like Li+ create a stable interfacial water layer. An optimal
Li+ ion concentration improves the HER on noble metals (such as Au) but affects the
HER on platinum group metals (PGMs) (such as Pt, Ir, and Pd) less favorably. Pt has a
greater affinity towards Li+ ions compared to Au, and, thus, strongly adsorbed Li+ ions can
block active sites of the Pt surface. In contrast, a high Li+ concentration near the electrode
boosts the breakdown of water, increasing the HER in unobstructed Au surfaces. These
observations indicate that manipulating the electrolyte composition offers the potential
for modifying noncovalent interactions and solvation dynamics at the electrified interface,
which could result in notable alterations in catalytic activity and selectivity.
The impact of electrolyte anions on the HER is debated; some studies find them
negligible, while others emphasize their substantial influence on the kinetics of the HER.
Anions can also adsorb on the electrode surface at potentials below the potential of zero
charge, especially in the H underpotential (HUPD ) region, affecting the M–Had energetics
and potentially reshaping the HER kinetics. Sulphate (HSO4 − and SO4 2− ) and chloride
(Cl− ) ions are known to affect the HER negatively. Conversely, HClO4 is suggested as an
ideal electrolyte for benchmarking and reporting activity and stability trends in rotating
disk electrode (RDE) measurements due to the neutral or beneficial impact of ClO4 − anions
on HER kinetics. Anionic contamination from SO3 − molecules during polymer electrolyte
membrane degradation is also known to negatively impact device performance and the
durability of electrolyzers, particularly at low PGM loadings.
Electrolyte impurities can also substantially impact the HER. Impurities can arise
from multiple origins: from commercial electrolytes (e.g., Zn in KOH), or from Pt and
Au counter-electrodes. Additionally, impurities can result from corrosion products due
to a corrosive electrochemical environment. Proton exchange membrane electrolysis and
alkaline electrolysis cells can contain two impurity types: exogenous and endogenous.
While electrolyzers require purified water, they may still contain slight levels of ionic species
and organic carbon as exogenous impurities. In industrial-scale operations, compromising
water quality and chemical selection can pollute electrocatalysts, posing a notable catalyst
deactivation challenge. On the other hand, endogenous impurities stem from internal
sources, often arising from gradual system deterioration and leaching in components.
Although some studies highlight the positive impact of trace metal impurities on the
HER activity of the substrate metal, electrolyte impurities are known to modify electrode
surfaces, affect reaction kinetics, and trigger undesired side reactions during the HER.
Therefore, for optimal HER performance, utilizing high-purity electrolytes and rigorous
quality control to minimize the impacts of impurities is essential. Moreover, employing
pure electrolytes when assessing electrocatalyst performance is sensible, as impurities
can either enhance or diminish the catalyst efficiency. Research suggests techniques such
as electrolyte pre-treatment, electrochemical purification, shielding of counter-electrodes,

and self-assembling and self-healing catalytically active films to mitigate the influence
of impurities.
Clearly, depicting a comprehensive view of the electrolyte effects on HER kinetics is
a difficult, if not impossible, task. However, it seems that a critical mass of fundamental
knowledge has been acquired, and optimizing electrolytes looks like a tangible approach to
boosting HER activity in the context of green hydrogen production. In fact, this could be the
most straightforward approach to increase the efficiency of existing electrolyzer systems,
as replacing electrolytes does not require a disruptive technology shift, while it can lead to
significant improvements in the efficiency of the water electrolysis process. The available
literature sources suggest a possible path towards achieving this goal. Namely, it seems
that a careful electrolyte optimization in terms of the concentration of structure-making
and structure-breaking cations (depending on the current densities that will be applied),
the use of anions that do not specifically adsorb and poison the catalyst surface, and the
rigorous control of the presence of impurities that have a detrimental effect on the activity
could be a viable route.
Nevertheless, to reach the mentioned goal, the anode side must be investigated as well.
That is, the electrolyte effects on the OER should be addressed, too. However, the OER is a
much more complex reaction than the HER. Here, we have mentioned several examples
of electrolyte effects on oxygen electrode reactions (both ORRs and OERs). Moreover,
the OER conditions are much harsher than the HER conditions. Thus, structural and
chemical changes in the anode can also induce electrolyte concentration and composition
changes in the interfacial region [148]. Due to its complexity, a comprehensive view of
electrolyte effects on the oxygen electrode can remain elusive for a long time. However, this
fact should not discourage future research in electrolyte engineering for improved water
electrolysis efficiency.
Finally, we note that the majority of experimental work on the electrolyte effects on
HER kinetics has been carried out using metallic electrodes. However, other types of HER
catalysts are actively investigated these days. Thus, a systematic analysis is also needed
for these materials, like carbon-based catalysts, sulfides, phosphides, nitrides, and others.
Moreover, the electrolyte effect could be particularly important in the case of single-atom
catalysts, and the community should delve into these important questions.
Author Contributions: Conceptualization, I.A.P. and G.K.G.; validation, I.A.P.; investigation, G.K.G.
and A.Z.J.; writing—original draft preparation, G.K.G. and A.Z.J.; writing—review and editing,
I.A.P.; visualization, G.K.G.; super-vision, I.A.P.; funding acquisition, I.A.P. All authors have read and
agreed to the published version of the manuscript.
Funding: This research was funded by the Serbian Science Fund, grant RatioCAT (PROMIS program).
A.Z.J and I.A.P. also acknowledge the financial support provided by the Serbian Ministry of Education,
Science, and Technological Development (Contract number: 451-03-47/2023-01/200146).
Data Availability Statement: There are no additional data to be shared.
Conflicts of Interest: The authors declare no conflict of interest.
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Review

The Effect of Electrolytes on the Kinetics of the Hydrogen

Hydrogen 2023, 4, 776–806. https://doi.org/10.3390/hydrogen4040049 https://www.mdpi.com/journal/hydrogen

H2 O2 − 2e− O2 + 2H+ Eo = 0.68 V (2)

H2 O − 2e− 1/2O2 + 2H+ Eo = 1.23 V (3)

2H+ + 2e− → H2 (4)

2H2 O + 2e− → H2 + 2OH− (5)

Hads + Hads → H2 + 2* (7)

H2 O + e− + * → Hads + OH− (9)

Hads + Hads → H2 + 2* (10)

H2 O + Hads + e− → H2 + OH− + * (11)

H3 O + + e − (H2 + )ad + OH− (12)

(H2 + )ad + e− H2 (13)

1.2. Importance of Studying the Kinetics of the HER

1.3. Definition and Types of Electrolytes Used in HER Studies

1.4. Significance of Electrolytes in HER Kinetics

2. Influence of Electrolyte Composition on HER Kinetics

of various electrocatalysts progressively declines with the rise in pH [50]. A significant

Hydrogen 2023, 4 784

et al. [101] conducted a study using surface-enhanced infrared absorption spectroscopy

2.2. Impact of Different Cations and Anions on HER Kinetics

Xue et al. [109] studied the role of different alkali-metal-cation-containing electrolytes

Applied Potential Duration Hydrogen Concentrationn Rate of Formation

electrolytes, we have determined the overpotential values required to achieve a current

2.3. Electrolyte Concentration and HER Kinetics

electrolyte solution. Both experimental and theoretical research revealed a volcano-shaped

2.4. Effect of Electrolyte Impurities

Figure 9. Diagrammatic representation of the impact of different types of impurities on PEMWEs.

H3 O+ ions restrict the HER activity in pH-neutral solutions at the electrode–electrolyte

as electrolyte pre-treatment, electrochemical purification, shielding of counter-electrodes,

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