Nano
Nano
Nano
Artificial Photosynthesis
Group members:
Akash Yadav 20045002
Ayush Jha 20045027
Sagar Goyal 20045108
Vaishnavi Farakte 20045045
Aditya Kumar Nayak 20045007
Motivation for the chosen topic
• In today’s world, a heavy reliance on fossil fuels poses major challenges regarding energy and environmental sustainability.
• Efficient use of solar energy offers a renewable path to address these issues.
• Solar energy irradiating the Earth's surface provides approximately 105 terawatts (TW), far exceeding the 20-40 TW global
power consumption expected by 2050.
• Efficient conversion and storage of solar energy is critical due to its intermittent nature.
• The photoelectrochemical (PEC) effect directly stores solar energy in chemical bonds, providing an efficient method of
conversion and storage.
• The use of nanomaterials, particularly one-dimensional nanowire morphology, introduces additional degrees of freedom
in optimizing PEC systems.
• Nanowires offer beneficial properties for system integration and optimization.
• This presentation summarizes research on nanowires utilizing PEC effects to store solar energy in chemical bonds.
Why nanowires ?
• Nanowires can be defined as structures that have a thickness or diameter constrained to tens of nanometers or less and an
unconstrained length.
Advantages as compared to its bulk counterparts:
• Light-Matter Interaction
o An oriented nanowire array, is a platform that provides a gradient of refractive index at the interface between the liquid and
semiconductors.
o This renders a nanowire array which suppresses reflection and enhances nondirectional scattering of incident light.
• Charge Separation
o Efficient charge separation lowers the recombination of photogenerated carriers and reduces the purity requirement of materials.
• Surface Area
o Nanowire morphology provides a surface area that is much larger than its bulk or planar counterparts and thereby offers more active
sites for the solar-driven reactions.
• Controlled Mass Transport within the Nanowire Array
o Nanowire array electrode can be considered as a special form of porous electrodes.
• Benefits for Device Integration
o Thanks to its large aspect ratio and the mechanical flexibility, nanowires can be readily processed through a variety of engineering
techniques, including roll printing, drop casting, and spin coating.
Photoelectrochemistry
• Photoelectrochemistry is an optoelectronic effect that occurs at
the interface of a semiconductor material and the liquid
electrolyte.
• When a semiconductor is in contact with liquid electrolyte, the
differences of Fermi levels between the semiconductor and
electrolyte will lead to the band bending at the interface as well
as the establishment of a built-in electric field.
• Under photon irradiation, additional electron-hole pairs are
generated and spatial separation of these photoexcited carriers
takes place thanks to the presence of the built-in electric field as
well as the relatively high mobility of these carriers.
• Among these electron-hole pairs, the photoexcited minority
carriers move toward the semiconductor/electrolyte interface,
while the majority carriers travel through the bulk of
semiconductor. A redox half-reaction that would not happen in
the absence of photon irradiation is initiated, thanks to the
accumulation of photoexcited minority carriers .
Coabsorbers
• Light absorption is ultimately determined by the bandgap of semiconductor materials.
• Common semiconductors in PEC applications, Like TiO2 and ZnO, only absorb UV part of solar light. Thus, coabsorbers
are used to widen the light absorption spectrum.
• Surface Bound Molecules and Complexes:
• Visible-light absorbing dye molecules can be adsorbed onto surface of the semiconductor for separation of photogenerated carriers.
• Metal Organic Frameworks (MOFs) show excellent photoresponse to visible light. It is observed that photocurrent could be improved
by nearly 100% under visible light using aminated MOFs.
• Metal Nanostructures:
• Plasmonic metal nanostructures show distinctive light absorption properties due to localized surface plasmon resonance effect. This
greatly enhances light absorption at specific wavelengths.
• By manipulating composition, shape, and size of plasmonic nanostructures, the plasmonic bands can be tuned from visible to near-IR
region. It is known that Ag and Au nanoparticles significantly enhance absorption and kinetics via this effect in nanowire PEC cells.
• Semiconductor Nanoparticles:
• To remedy the limited light absorption of a single semiconductor material in photoelectrochemistry, semiconductor heterojunctions
are constructed.
• Here, the favorable band alignment among these semiconductors leads to effective light absorption as well as efficient charge
separation, which provides a much higher photocurrent density under simulated sunlight.
Catalysts
• Catalysts are combined with nanowires to boost the half-reactions of oxidation and reduction and suppress the possible
charge recombination and reverse reactions at the semiconductors’ surface.
• Molecular/Cluster as Catalysts:
• These catalysts with earth-abundant elements possess advantages of definite and designable structures, tunable redox properties, and
potential links to material surface, rendering them suitable as catalysts for nanowires.
• These catalysts seem to be less stable under oxidative environment, they are more often applied to photocathodes rather than
photoanodes. At the photocathode, Si is the most popular semiconductor material studied.
• Inorganic Materials as Catalysts:
• Both photocathodes and photoanodes can employ various inorganic materials to boost the catalytic performance, thanks to their
tunable structural and electronic properties.
• Precious metals such as Pt are still widely applied for many electrochemical reactions In the case of nanowire photocathode, Pt is the
widely used catalyst for hydrogen evolution with Si, GaN, and GaP semiconductor nanowires.
• Biological Moieties as Catalysts:
• Biological entities often exhibit high selectivity toward a specific reaction process. But, they have low efficiency of 0.5% to 2.0%.
• inorganic semiconductors can have efficiencies up to 20%. Using an inorganic-biological can take the strengths of both and achieve an
efficient and selective process of artificial photosynthesis.
• A Si nanowire array was used to study the interactions between Si nanowires and Shewanella oneidensis MR-1. It recognized the
surroundings and modified its swimming and early stage attachment to the nanowire. The physical interaction was sensitive to the local
environment, ionic strength of the electrolyte and the gas pressure in the headspace.
Mimicking the Microscopic Assembly of Natural
Photosynthesis
Dual Semiconductor Integration:
• Mimicking the natural "Z-scheme" in photosynthesis, artificial photosynthesis
requires integrating two light-absorbers (semiconductor materials) with well-
aligned bands to conduct the photoanodic and photocathodic reactions.
• This setup aims to store solar energy in chemical bonds without additional
energy supply, allowing one semiconductor to function as photoanode for
oxidation and another as photocathode for reduction.
Ohmic Contact and Charge Movement:
• Establishing an ohmic contact between the two semiconductors enables the
flow of charge carriers between them.
• Under sunlight irradiation, photoexcited minority carriers move to the
electrode/electrolyte interface for catalytic reactions, while the majority
carriers recombine at the ohmic contact to complete the circuit.
Optimization:
• Achieving maximum solar-to-hydrogen efficiency requires matching the
operating current densities (Jop) of the photoanode and photocathode as
closely as possible to their maximum power points (PPA and PPC).
Mimicking the Microscopic Assembly of Natural
Photosynthesis
Optimal Band Gaps and Alignments:
• Achieving high energy efficiency in the system requires selecting
photoelectrodes with suitable band gaps.
• Theoretical predictions suggest optimal band gaps for photoelectrodes
at approximately 1.1 and 1.7 eV.
Nanowire Morphology:
• Use of nanowire morphology can help with challenges such as limited
material options by reducing overpotential for charge transfer at the
surface.
• An asymmetric nanowire composed of a silicon core and TiO2 shell
(Si/TiO2) was proposed to demonstrate solar-driven water splitting.
• A tree-shaped Si/TiO2 nanosystem was created, combining light
absorption, charge separation, and chemical reactions, resulting in a
system with significantly higher activity.
• Combinations such as InP nanowires and nanoporous BiVO4
photoanode materials have been explored for unassisted solar water-
splitting, showing promising solar-to-fuel efficiency.
Challenges, and future research scope
Challenges:
• Lack of a refined model at the nanoscale level for photoelectrochemical processes, particularly regarding the impact of
catalyst presence on local band bending.
• Difficulty in determining the optimal distance among loaded catalyst nanoparticles on the surface for efficient charge
transfer and high turnover rates.
• Fine-tuning interfacial interactions between nanowires and various catalysts, molecules, and biocatalysts for enhanced
performance.
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