Catalysis Letters (2024) 154:1828–1838

https://doi.org/10.1007/s10562-023-04433-9

Synthesis of a New Bimetallic Metal–Organic Framework Based

on ­La3+ and ­Ce3+ as New Porous Materials for the Electrooxidation
of Acetaminophen
Alireza Ansari Moghadam1 · Alireza Rezvani1 · Hamideh Saravani1 · Mehdi Shahbakhsh1 · Ghasem Sargazi2

Received: 28 May 2023 / Accepted: 26 July 2023 / Published online: 19 August 2023
© The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2023

Abstract
For the first time, a bimetallic metal–organic framework of (MOF) L ­ a3+ and C
­ e3+ (Ce, La-MOF) was synthesized using
a new solvothermal route. Also, monometallic MOFs ­La (La-MOF) and ­Ce3+ (Ce-MOF) were synthesized using the
3+

mentioned method. To identify, and analyze the synthesized nanostructures, field emission scanning microscopy (FSEM),
energy dispersive X-ray mapping (MAP), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), thermal
gravity curve (TGA), differential scanning calorimetry (DSC) analysis, Fourier transforms infrared (FT-IR) spectroscopy
and Brunauer–Emmt–Teller surface area (BET) were used. According to the XRD diffraction patterns of Ce–La-MOF
nanostructure, no additional peaks are derived from La species, which confirms that the addition of La does not change the
crystalline phase structure of Ce-MOF. The size of La-MOF, Ce-MOF, and Ce, La-MOF nanostructures was calculated by the
Williamson-Hall method and reported as 72.97, 55.46, and 81.55 nm, respectively. The specific surface area (BET) results for
La-MOF, Ce-MOF, and Ce, La-MOF nanostructures were reported as 140, 200, and 260 m ­ 2 ­g−1 respectively, and the mean
3
pore volumes of the nanostructures were reported as 0.019, 0.022 and 0.030 ­cm respectively. These values allow the use
of these versatile nanostructures in various applications such as biosensing, separation and purification, medicine field, and
catalysts. In addition, in this study, modified electrodes for synthesized nanostructures were tested for the electrooxidation
of acetaminophen. And the obtained results show better electrocatalytic behavior of bimetallic Ce, La-MOF nanostructures
than monometallic La-MOF, Ce-MOF nanostructures against acetaminophen.

* Alireza Rezvani
ali@hamoon.usb.ac.ir
1
Department of Chemistry, Faculty of Basic Sciences,
University of Sistan and Baluchestan, Zahedan, Iran
2
Noncommunicable Diseases Research Center, Bam
University of Medical Sciences, Bam, Iran

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Synthesis of a New Bimetallic Metal–Organic Framework Based on ­La3+ and ­Ce3+ as New Porous… 1829

Graphical Abstract

Keywords Solvothermal method · Williamson-Hall method · Bimetallic · La-MOF · Ce-MOF · Acetaminophen ·

Electrooxidation

1 Introduction 6]. There are two structural components in MOFs: clusters

or metal ions and organic binders that create porous and
Recently, the synthesis of micro and meso-porous materi- regular structures. Various combinations of these building
als and metal–organic framework nanostructures (MOFs) blocks have led to the creation of a large number of MOFs
attracted the attention of scientists [1]. Due to the char- [7, 8]. Various synthesis methods have been reported for
acteristics of these materials and the role they had in the MOFs, the most common of which are solvothermal, micro-
daily life of humans, as well as the impact they will have wave, mechanochemical, sonochemical, and electrochemical
on the future of human technology, they were more wel- synthesis methods [9, 10]. solvothermal synthesis is con-
comed. Metal–organic framework nanostructures (MOFs) sidered a powerful method in the production of nanoma-
are a new class of porous hybrid materials, which are formed terials. Usually, solvothermal synthesis of MOFs with dif-
through the self-assembly of metal ions/clusters and organic ferent metal ions and organic links provides the possibility
ligands [2–4]. Unlike other porous materials such as zeo- of fine-tuning the crystal structures and the composition of
lites, activated carbon, metal complex hydrides, etc., MOFs functional groups designed for specific applications. There-
have many characteristics such as ease of synthesis, high fore, by using different metal centers or organic ligands, the
surface area, structural diversity, flexibility, high selectivity, properties, size, and function of the cavity of these porous
thermal stability, very low density, selective absorption [5, materials can be optimized [11–13]. Outstanding features

13
1830 A. A. Moghadam et al.

of this method are high efficiency, favorable controllabil- of ACM in biological fluids (blood serum and urine sam-
ity, and biocompatibility [14, 15]. By changing the reaction ples) is of particular importance [29–32]. So far, various
conditions and using suitable solutions, additives, molds, methods have been used to measure it, such as UV, HPLC,
and substrates, as well as by properly energizing the system, and electrochemical methods. But electrochemical methods
a wide range of nanostructures with desirable quality and are more suitable for ACM measurement due to their high
dimensions can be produced. These properties make porous speed, sensitivity, and selectivity [33–36]. Existing com-
metal–organic frameworks suitable candidates for chemi- mercial electrodes have low sensitivity and low selection.
cal reactions [16, 17]. In recent years, significant research Therefore, to increase the selectivity and sensitivity, their
has been done to introduce new features or to optimize the surface must be modified with an appropriate electrocatalyst.
structural features and porous nature of MOFs. The most As far as we know, there is no published report on Ce,
important applications can be mentioned in catalytic fields, La-MOF bimetallic nanostructure, and this report is the first
biosensing, separation and purification, medicine field, and report on the synthesis of Ce, La-MOF bimetallic nano-
other fields [18, 19]. structure. In this research, the solvothermal method with
Recently, to increase the catalytic, electronic, and lumi- optimal physicochemical properties was used to synthesize
nescence properties in metal–organic framework nodes, a new Ce, La-MOF bimetallic nanostructure, and then it
adding second metal ions to them has been proposed to was compared with the synthesized monometallic La-MOF
synthesize bimetallic MOFs. In this type of MOFs, two dif- and Ce-MOF nanostructures. The potential of modified
ferent metal ions are added to a structure, which increases electrodes with synthesized nanostructures was tested for
the stability of the structure and improves the performance the electrochemical detection of ACM. And the obtained
of bimetallic MOFs [12, 13, 20–22]. Bimetallic MOFs have results showed better electrocatalytic behavior of Ce–La-
more comprehensive applications in various fields such as MOF bimetallic nanostructures than monometallic La-MOF,
gas sensing, separation and storage, drug delivery, and cata- Ce-MOF nanostructures against ACM.
lysts than monometallic MOFs [22–24]. Bimetallic MOFs
have been widely used in energy conversion and storage,
such as lithium-ion batteries, supercapacitors, fuel cells, 2 Experimental Section
solar cells, and Li–S batteries, in which MOFs act as elec-
trode materials. Bimetallic MOFs may provide different cat- 2.1 Materials
alytic activities in spatial proximity in heterogeneous cataly-
sis and improve water stability and thermal stability [12]. La(NO3)3·6H2O Mw: 433.01 g/mol, 99.9%, Ce(NO3)3·6H2O
They also show more stability and desulfurization capacity Mw: 434.22 g/mol, 99%, benzene-1,3,5-tricarboxylic acid
than monometallic MOFs and also zeolites. Also, in similar ­[C9H6O6 ­(H3BTC)] Mw: 210.14 g/mol, 98%, DMF, 99.8%,
studies, when bimetallic MOFs are used as heterogeneous ­CH3CH2OH, 99.7%, and graphite powder. All materials
catalysts, they show better catalytic activities than monome- were purchased from Sigma (www.​sigm.​com) and used
tallic MOFs [25, 26]. In industry, the most significant cata- directly without any purification.
lytic actions occur through heterogeneous catalysis, which
includes reactants and products in the gas or liquid phase and 2.2 Catalyst Synthesis
catalysts in the solid phase. In heterogeneous catalysis, the
reactions occur at the interface between the catalyst support The synthesis of La-MOF was carried out by the solvo-
and the reactant molecules. Due to the distinct pore struc- thermal method as follows: for this purpose, in one flask,
ture and tunable chemical composition of bimetallic MOFs, 0.6 mmol of lanthanum (III) nitrate hexahydrate in 20 ml
they are ideal precursors for the preparation of catalysts, of ultrapure water, and the other flask, 0.3 mmol of BTC in
and with their synthesis, the electrocatalytic performance water. A solution of ethanol and DMF (40 ml, volume ratio
of MOFs has been improved. Transition metal MOFs have 1:1) was dissolved on a heater at room temperature under
been established and thoroughly investigated as promising continuous stirring for 60 min. Then, the solution con-
catalysts due to their tunable crystal structure [22, 27, 28]. taining BTC was slowly added to the lanthanum solution
This article deals with the development and synthesis of and stirred continuously for 30 min at room temperature
bimetallic Ce, La-MOF and its electrocatalytic application. and it was sufficiently dissolved. The resulting aqueous
Acetaminophen (N-acetyl-aminophenol, ACM) is a non- slurry mixture was transferred to a 100 ml stainless steel
narcotic, analgesic, and antipyretic drug with a solubility of autoclave with Teflon coating and subjected to hydrother-
12,900 mg/L. A large amount of about 1.45 × ­105 tons of mal treatment in an oven with a temperature of 120 °C
ACM is produced and consumed annually. ACM is used to for 24 h. After the solvothermal reaction, the materials
reduce pains such as headaches, colds, flu and mild pains were separated by centrifugation and washed and purified
such as joint and muscle pain. Therefore, the measurement several times with aqueous ethanol and DMF and finally

13
Synthesis of a New Bimetallic Metal–Organic Framework Based on ­La3+ and ­Ce3+ as New Porous… 1831

dried at 100 °C for 12 h. Synthesis of Ce-MOF was carried of other materials was similar to the synthesis of La-MOF.
out similarly to La-MOF. As well as the synthesis of La, Figure 1A shows the synthesis process of catalysts. Also,
Ce-MOF, 0.3 mmol of lanthanum nitrate hexahydrate (III) the probable structure of La-MOF, Ce-MOF, Ce, La-
and 0.3 mmol of cerium nitrate hexahydrate (III) were dis- MOF nanostructures in optimal hydrothermal conditions
solved together in 20 ml of ultrapure water. The addition is shown in Fig. 1B.

Fig. 1  A Schematic formation of La-MOF (a), Ce-MOF (b), Ce, La-MOF (c) nanostructures. B The probable structure of La-MOF, Ce-MOF,
Ce, La-MOF nanostructures

13
1832 A. A. Moghadam et al.

2.3 Instrumentations 3.1.1 Williamson‑Hall (W‑H) Analysis

For efficient identification of materials by analysis, X-ray The XRD peak broadening effect caused by strain can be
diffraction [XRD, Model D/MAX2500, Rigaku, (http://​ used to calculate the intrinsic strain along with the size of the
www.​rigaku.​com/​en)], field emission electron microscopy MOFs, in the Williamson-Hall method, Warren-Auerbach
(FESEM), and energy dispersive spectrum (EDS/MAP) method, etc. In the Williamson-Hall method, calculating the
X-ray spectroscopy [MIRA3 TECAN-XMU (http://​www.​ intrinsic strain and the size of MOFs is easier and simpler
tescan.​com)], (TGA) thermal analysis [SDT Q600 SPECI- than other methods [41, 42]. The physical broadening of the
FICATIONS (http://​w ww.​t ains​t rume​n ts.​c om)], (FTIR) X-ray diffraction peak is due to the size and microstrain of
Fourier transform infrared spectroscopy [SHIMADZU nanoparticles and total broadening, which can be written as
FT8400S (http://​www.​labx.​com)] and technique (BET) follows using the W-H method:
Brunauer Emmett Teller [BELSORPMINI II (http://​www.​
labwr​ench.​com)] used (before measurement, all the samples
𝛽total = 𝛽size + 𝛽strain (1)
were degassed at 110 C under high vacuum for 8 h). To per- In this research, the modified W-H equation, the Wil-
form electrochemical experiments, a SAMA500 electroana- liamson-Hall uniform deformation model (UDM) was used
lyzer (SAMA Research Center, Iran) was used that equipped to calculate the average particle size and microstrain, which
with a three-electrode system consisting of an unmodified will be discussed in the next section.
or modified graphite paste electrode (CPE) as the working
electrode, a platinum electrode as an auxiliary electrode, and 3.1.1.1 Williamson‑Hall Uniform Deformation Model
a silver/silver chloride (Ag/AgCl) electrode as the reference (UDM) In the UDM model, the uniform strain caused by
electrode. crystal defects in nanoparticles is introduced and considered
throughout the crystallographic directions. In other words,
2.4 Modified Electrodes Preparation UDM considers an isotropic strain [43, 44]. As a result, this
inherent strain affects the physical broadening of the XRD
To make a La-MOF-modified carbon paste electrode; 192 profile, and the inherent strain-induced peak broadening is
mg of graphite powder, 8 mg of La-MOF, and 50 mg of par- expressed as follows:
affin oil were mixed. The resulting mixture was ground in a
mortar for 15 min. Then it was packed in a glass tube with a 𝛽strain = 4𝜀tan𝜃 (2)
cross-section (A = 0.22 ­cm2) with the help of a copper wire
which can be expressed as the total broadening due to strain
(for contact and electrical conductivity). The name of the
as well as the size in a specific peak with 𝛽hkl as follows:
prepared electrode was CPE/La-MOF. Also, two modified
carbon paste electrodes Ce-MOF and Ce, La-MOF similar 𝛽hkl = 𝛽size + 𝛽strain (3)
to the modified carbon paste electrode La-MOF were pre-
pared with the names CPE/Ce-MOF and CPE/Ce, La-MOF In the part where 𝛽hkl shows the full width of the maxi-
respectively. And finally, to compare the electrodes, like mum intensity, it can be written as follows:
the previous three electrodes, a bare carbon paste electrode K𝜆 1
(BCPE) was prepared with a mixture of 200 mg of graphite 𝛽hkl = .
D𝜈 cos𝜃
+ 4𝜀tan𝜃 (4)
and 50 mg of paraffin oil.
On re-arranging, this Eq. (7) will be,
K𝜆
3 Results and Discussions 𝛽hkl ⋅ cos𝜃 = + 4𝜀 ⋅ sin𝜃 (5)
D𝜈
3.1 X‑Ray Diffraction Analysis The UDM equation is a straight-line equation, which
takes into account the isotropic nature of crystals. K is the
XRD analysis was performed to determine the crystalline shape factor equal to 0.9, λ is the wavelength of X-ray radia-
size distribution, phase structure, and crystallinity (Fig. 2D) tion for Cu Kα radiation equal to 0.154056 nm, D ­ v is the
of La-MOF, Ce-MOF, and Ce–La-MOF nanostructures. All, crystallite, θ is the Bragg angle, and 𝛽hkl is full width at
these MOFs, present the same XRD diffraction patterns half-peak height (FWHM) and ε is the strain. Therefore,
based on which characteristic peaks are seen at (2θ) 8.93, by plotting the values of β·cos(θ) along the Y-axis against
10.81, 12.57, 16.84, 23.61, and 29.01 [37–40] indicating the values of 4sin(θ) along the X-axis and using the opti-
that incorporation of La or Ce ions in the structure of MOF mal line equation shown in Fig. S1A–C, the size of the
(bimetallic MOFs), does not change the crystalline structure nanocrystals and the internal strain values of the lattice can
of the related monometallic MOFs.

13
Synthesis of a New Bimetallic Metal–Organic Framework Based on ­La3+ and ­Ce3+ as New Porous… 1833

A B

C D

Ce,La-MOF
Intensity/(a.u.)

Ce-MOF

La-MOF

5 15 25 35 45 55 65 75
2Theta/degree

Fig. 2  FESEM images of La-MOF (A), Ce-MOF (B), and La, Ce-MOF (C) nanostructures. XRD patterns of La-MOF, Ce-MOF, and Ce, La-
MOF (D) prepared by solvothermal conditions

Table 1  Crystallite size and lattice strain as determined from the Wil- Fig. 2A–C. In the synthesis of this method, the optimal con-
liamson‐Hall plots for La-MOF, Ce-MOF, and La, Ce-MOF nano- ditions caused the desired morphology and uniform distribu-
structures
tion of nanostructures without aggregation, and the average
La-MOF Ce-MOF La, Ce-MOF particle size of La-MOF, Ce-MOF, and La, Ce-MOF nano-
particles was 72.97, 55.46, and 82.55 nm, respectively. All
Crystallite size, nm 72.97 55.46 81.55
Williamson-Hall method samples are tending to rod-shaped with stable morphology
Lattice strain, % 0.13 0.21 0.09 as can be seen in the figures. This stability can be related to
the efficient synthesis route, type of MOF and configuration
of final structure. Also, Fig. 4c shows that the MOF structure
be determined. These values are summarized in Table 1. is preserved after loading La on Ce. Figure S2A–C shows
Because in the Williamson-Hall method, two strain factors the EDS elemental analysis for La-MOF and Ce-MOF mon-
and particle size are checked simultaneously, it has higher ometallic nanostructures and Ce, La-MOF bimetallic nano-
accuracy. structure. In addition, Fig. S2D–F is related to the elemental
analysis of the EDS spectrum, and it shows the presence of
3.2 Morphology, Size Distribution, and EDS Analysis La, O, and C elements in the La-MOF monometallic nano-
structure, Ce, O and C elements in the Ce-MOF monometal-
FESEM images of La-MOF, Ce-MOF, and La, Ce-MOF lic nanostructure, as well as La, Ce, O and C elements in the
synthesized by the solvothermal method are shown in Ce–La-MOF bimetallic nanostructure.

13
1834 A. A. Moghadam et al.

3.3 Thermodynamic Behavior 400 °C with 27.1% weight loss is related to the destruction
of the 1,3,5-H3BTC ligand, and its oxidation causes the col-
To thermally analyze the prepared samples, TGA- DSC lapse of the crystal structure. And also for the La, Ce-MOF
analyses were performed, which is shown in Fig. 3A–C. For sample, three distinct peaks are observed in the DSC profile
the La-MOF sample, three distinct endothermic peaks are (Fig. 3C), which is associated with weight loss in the TGA
observed in the DSC profile (Fig. 3A), which is associated curve. The first peak in the DSC curve at 25–200 °C with
with weight loss in the TGA curve. The first peak in the DSC 8.6% weight loss is related to physically absorbed water.
curve at 25–200 °C with 7.2% weight loss is due to physi- In the DSC curve, the second peak at the temperature of
cally adsorbed water. In the DSC curve, the second peak at 300–370 °C with 12.5% weight loss is related to DMF sol-
the temperature of 300–370 °C with 10.9% weight loss is vent and water coordinated with MOF pores. And the third
related to DMF solvent and water coordinated with MOF peak in the DSC curve at a temperature higher than 400 °C
pores. And the third peak in the DSC curve at a tempera- with 26.4% weight loss is related to the destruction of the
ture higher than 400 °C with 15.2% weight loss is related 1,3,5-H3BTC ligand, and its oxidation causes the collapse
to the destruction of the 1,3,5-H3BTC ligand, and its oxida- of the crystal structure.
tion causes the collapse of the crystal structure. And for
the Ce-MOF sample, three distinct peaks are observed in 3.4 FTIR Spectra
the DSC profile (Fig. 3B), which is associated with weight
loss in the TGA curve. The first peak in the DSC curve at The FT-IR spectra of the synthesized La-MOF, Ce-MOF,
25–200 °C with 10.3% weight loss is related to physically and Ce, La-MOF samples are shown in Fig. 3D. For La-
absorbed water. In the DSC curve, the second peak at the MOF, asymmetric and symmetric stretching bands cor-
temperature of 300–370 °C with 19.9% weight loss is related responding to –OCO– appeared at around 1607 and 1378
to DMF solvent and water coordinated with MOF pores. And ­cm−1. C=C stretching bands of aromatic rings were observed
the third peak in the DSC curve at a temperature higher than near 1528 and 1431 ­cm−1. And an O–H board peak at 3467

10
110 2
A 100 B
100 1 5

Heat Flow (W/g)

Heat Flow (W/g)

0
80
Weight (%)

90
Weight (%)

-1 0
80
-2 60 -5
70 TGA La-BTC
-3
TGA Ce-BTC
DSC La-BTC DSC Ce-BTC

60 -4 40 -10
0 200 400 600 0 200 400 600
Temperature(°C) Temperature(°C)

5
100 C La-MOF D
0 Ce-MOF
Heat Flow (W/g)

La,Ce-MOF

80
Weight (%)

-5

60 -10
TGA Ce,La-BTC
DSC Ce,La-BTC
40 -15
0 200 400 600 3300 2300 1300 300
Temperature(°C) Wavenumber (Cm-1)

Fig. 3  TGA and DSC curve analysis of the La-MOF (A), Ce-MOF (B), and La, Ce-MOF (C). FTIR spectra of benzene-1, 3, 5-tricarboxylic acid
(ligand), La-MOF, Ce-MOF, and La, Ce-MOF nanostructures (D) prepared by solvothermal conditions

13
Synthesis of a New Bimetallic Metal–Organic Framework Based on ­La3+ and ­Ce3+ as New Porous… 1835

­cm−1 was attributed to water molecules that may be physi- c­ m−1. C=C stretching bands of aromatic rings were observed
cally adsorbed or attached to the sample. Also, low-intensity at 1535 and 1435 ­cm−1. And an O–H stretching band at 3422
bands related to La–O stretching vibrations were observed ­cm−1 was attributed to water molecules that may be physi-
at 412 ­cm−1 [45]. For Ce-MOF, asymmetric and symmetric cally adsorbed or attached to the sample. Also, low-intensity
stretching bands corresponding to –OCO– appeared around bands related to La–O and Ce–O stretching vibrations were
1611 and 1370 ­cm−1. C=C stretching bands of aromatic observed at 415 and 529 c­ m−1, respectively. These peaks
rings were observed at 1531 and 1437 ­cm−1. And an O–H have good coordination between L ­ a3+ and ­Ce3+ with 1,3,5-
stretching band at 3427 ­cm−1 was attributed to water mol- H3BTC ligand and also maintain negligible changes after
ecules, which may be physically adsorbed or attached to the adsorption, which indicates the structural integrity of the
sample. Also, low-intensity bands related to Ce–O stretch- bimetallic Ce, La-MOF.
ing vibrations were observed at 529 c­ m−1 [46]. And also for
Ce, La-MOF, asymmetric and symmetric stretching bands 3.5 Textural Properties
corresponding to –OCO– appeared around 1611 and 1371
N2 adsorption/desorption isotherm at 77K was used to deter-
mine the textural properties including specific surface area
Table 2  BET results for La-MOF, Ce-MOF, and La, Ce-MOF nano-
structures and mean pore volume of the nanostructures. The results of
the specific surface area (BET) of La-MOF, Ce-MOF, and
Vm as, BET Total pore volume Mean Ce, La-MOF nanostructures were given in detail in Table 2.
((cm3 ­g−1) (m2 ­g−1) (cm3 g­ −1) pore
diameter The specific surface area of La-MOF, Ce-MOF, and Ce, La-
(nm) MOF nanostructures is 140, 200, and 260 m ­ 2 ­g−1, respec-
tively, and the mean pore volume of La-MOF, Ce-MOF, and
La-MOF 1.1484 140 0.019141 15.318
Ce, La-MOF nanostructures is 0.019, 0.022 and 0.030 c­ m3
Ce-MOF 1.365 200 0.022629 18.185
­g−1, respectively. As seen in Fig. 4A–C, with the increase in
La, Ce-MOF 1.1436 260 0.030501 20.535
relative pressure, the curves related to nanostructures show

200
150
ADS A B
Va/cm3(STP) g-1

150 ADS
DES DES
Va/cm3(STP) g-1

100
100

50
50

0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
p/p0 p/p0

35 Graghite
300 ADS
C 25
Ce-MOF
La-MOF
D
DES
Va/cm3(STP) g-1

La,Ce-MOF

200 15
I / µA

5
100
-5

0 -15
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
p/p0 E / V vs.Ag/AgCl

Fig. 4  Adsorption/desorption isotherms of La-MOF (A), Ce-MOF (B), and La, Ce-MOF (C) nanostructures synthesized by solvothermal condi-
tions. D CVs of BCPE, CPE/la MOF, CPE/ Ce MOF, and CPE/ La-Ce MOF in 0.1 M PBS (pH = 2, scan rate = 100 mV ­s−1)03

13
1836 A. A. Moghadam et al.

a behavior similar to type IV isotherm. So, based on the in the synthesis of bimetallic MOF nanostructures as well
IUPAC classification [47, 48], the samples studied in this as monometallic MOF nanostructures. Their structure and
research have type IV isotherm and its residual loop is also morphology were determined by various techniques such as
of type ­H3, which applies to nanostructures. FESEM, XRD, BET, etc., which show that the synthesized
bimetallic MOFs (Ce, La-MOF) have characteristics such as
3.6 Electro‑catalytic Performance of La‑MOF, high porosity, stability, better surface area as well as more
Ce‑MOF, and Ce, La‑MOF accessible active functional sites. The obtained results show
that the electrocatalytic behavior of Ce, La-MOF bimetallic
To evaluate the electrocatalytic activity of La-MOF, Ce- nanostructures has a higher electrocatalytic activity against
MOF, and La, Ce-MOF nanostructures, cyclic voltammetry acetaminophen than La-MOF, Ce-MOF monometallic nano-
was taken. To prepare the carbon paste electrode, a mixture structures. The simplicity of the route for preparing bimetal-
of 195 mg of graphite powder, 5 mg of La-MOF, and 50 mg lic MOF nanostructures is an important advantage for them.
of paraffin oil was prepared. The mixture was ground in a This makes bimetallic MOFs be considered a new class of
mortar for 10 min and a homogeneous paste was obtained. efficient nanostructures for energy conversion and storage.
Finally, it was packed in a glass tube (A = 0.22 c­ m2) for Also, due to the wide variety of MOF structures and the vari-
electrical contact with copper wire. In the next step, Ce- ous possibilities that these materials offer to introduce added
MOF and La-Ce-MOF modified carbon paste electrodes metals by substitution or integration, it can be predicted that
were prepared with same protocol. These electrodes were this area will grow in the near future to improve the perfor-
called CPE/La-MOF, CPE/Ce-MOF, and CPE/La-Ce-MOF. mance of bimetallic MOFs and used them in various fields
For comparison, a bare carbon paste electrode (BCPE) was such as gas separation, measurement, energy storage and
also fabricated using the same protocol. The results were conversion, and catalysis.
discussed in detail. In Fig. 4D, the CV of BCPE (in 0.1
Supplementary Information The online version contains supplemen-
M phosphate buffer solution containing 100 μM acetami- tary material available at https://d​ oi.o​ rg/1​ 0.1​ 007/s​ 10562-0​ 23-0​ 4433-9.
nophen) shows the anodic (Ia) and cathodic (Ic) redox peaks
at 0.710 and 0.588 V, respectively (∆Ep = 0. 122 V) with
the peak currents of 4.1 and 2 µA, respectively. For CPE/
La-MOF, the redox peaks were seen at 0.635 and 0.581 V, References
respectively (∆Ep = 0.054 V) with the peak currents of 8.6
and 2.5 µA, respectively. And also for CPE/Ce-MOF, the 1. Yang F, Du M, Yin K, Qiu Z, Zhao J, Liu C, Zhang G, Gao Y,
CV curve shows redox peaks at 0.70 and 0.630 V, respec- Pang H (2022) Applications of metal-organic frameworks in water
tively (∆Ep = 0.070 V) with the peak currents of 9.6 and 4.0 treatment: a review. Small 18:2105715
2. Shen Y, Pan T, Wang L, Ren Z, Zhang W, Huo F (2021) Program-
μA, respectively. For CPE/La, Ce-MOF, the redox peaks mable logic in metal–organic frameworks for catalysis. Adv Mater
were seen at 0.657 and 0.631 V, respectively (∆Ep = 0.026 33:2007442
V) with the peak currents of 13.4 and 4.8 μA, respectively. 3. Shu JC, Cao WQ, Cao MS (2021) Diverse metal–organic frame-
CPE/La, Ce-MOF shows maximum peak currents and the work architectures for electromagnetic absorbers and shielding.
Adv Funct Mater 31:2100470
lowest ∆Ep for acetaminophen. In the CPE/La, Ce-MOF, 4. Kumari V, Singh PP, Kaushal S (2022) Synthesis and applications
the presence of both La and Ce ions enhances the electro- of metal-organic frameworks and graphene-based composites: a
static force and exerts a strong attraction force toward aceta- review. Polyhedron 214:115645
minophen molecules results in facilitated electron transfer. 5. Mohanty A, Jaihindh D, Fu Y-P, Senanayak SP, Mende LS, Rama-
doss A (2021) An extensive review on three dimension architec-
Moreover, its large surface area (compared to other elec- tural metal-organic frameworks towards supercapacitor applica-
trodes) results in the accumulation of more acetaminophen tion. J Power Sources 488:229444
molecules on the surface of the electrode. As a result, CPE/ 6. Zhang Y, Liu S, Zhao Z-S, Wang Z, Zhang R, Liu L, Han Z-B
La, Ce-MOF shows higher peak currents and lower ∆Ep for (2021) Recent progress in lanthanide metal–organic frameworks
and their derivatives in catalytic applications. Inorg Chem Front
acetaminophen compared to other electrodes. 8:590–619
7. Cai G, Yan P, Zhang L, Zhou H-C, Jiang H-L (2021) Metal–
organic framework-based hierarchically porous materials: synthe-
4 Conclusion sis and applications. Chem Rev 121:12278–12326
8. Dutta A, Pan Y, Liu J-Q, Kumar A (2021) Multicomponent iso-
reticular metal-organic frameworks: principles, current status and
In this research, the optimized solvothermal route was used challenges. Coord Chem Rev 445:214074
to synthesize new bimetallic nanostructures Ce, La-MOF, 9. Mahreni M, Ristianingsih Y (2020) A review on metal-organic
and monometallic nanostructures La-MOF and Ce-MOF. framework (MOF): synthesis and solid catalyst applications. In:
Proceeding of LPPM UPN “Veteran” Yogyakarta conference
Optimum solvothermal conditions (insulated autoclave, oven series 2020–engineering and science series, pp 638–645
temperature: 120 °C, duration: 24 h) play an important role

13
Synthesis of a New Bimetallic Metal–Organic Framework Based on ­La3+ and ­Ce3+ as New Porous… 1837

10. Sud D, Kaur G (2021) A comprehensive review on synthetic of imidacloprid pesticide and cadmium ions from wastewater.
approaches for metal-organic frameworks: from traditional sol- Chemosphere 272:129648
vothermal to greener protocols. Polyhedron 193:114897 29. Abdullah N, Fulazzaky MA, Yong EL, Yuzir A, Sallis P (2016)
11. Krap CP, Newby R, Dhakshinamoorthy A, García H, Cebula I, Assessing the treatment of acetaminophen-contaminated brew-
Easun TL, Savage M, Eyley JE, Gao S, Blake AJ (2016) Enhance- ery wastewater by an anaerobic packed-bed reactor. J Environ
ment of ­CO2 adsorption and catalytic properties by Fe-doping of Manage 168:273–279
­[Ga2(OH)2(L)](H4L= biphenyl-3, 3′, 5, 5′-tetracarboxylic acid), 30. Wang S, Wu J, Lu X, Xu W, Gong Q, Ding J, Dan B, Xie P
MFM-300 (Ga2). Inorg Chem 55:1076–1088 (2019) Removal of acetaminophen in the F ­ e2+/persulfate sys-
12. Masoomi MY, Morsali A, Dhakshinamoorthy A, Garcia H (2019) tem: kinetic model and degradation pathways. Chem Eng J
Mixed-metal MOFs: unique opportunities in metal–organic 358:1091–1100
framework (MOF) functionality and design. Angew Chem 31. Li Y, Song W, Fu W, Tsang DC, Yang X (2015) The roles of
131:15330–15347 halides in the acetaminophen degradation by UV/H 2O2 treat-
13. Dhakshinamoorthy A, Asiri AM, Garcia H (2016) Mixed-metal ment: kinetics, mechanisms, and products analysis. Chem Eng J
or mixed-linker metal organic frameworks as heterogeneous cata- 271:214–222
lysts. Catal Sci Technol 6:5238–5261 32. Moradi S, Isari AA, Hayati F, Kalantary RR, Kakavandi B (2021)
14. Elahi N, Rizwan M (2021) Progress and prospects of magnetic Co-implanting of T ­ iO2 and liquid-phase-delaminated g-C3N4 on
iron oxide nanoparticles in biomedical applications: a review. multi-functional graphene nanobridges for enhancing photocata-
Artif Organs 45:1272–1299 lytic degradation of acetaminophen. Chem Eng J 414:128618
15. Kong X, Liu X, Zheng Y, Chu PK, Zhang Y, Wu S (2021) Gra- 33. Sohouli E, Shahdost-Fard F, Rahimi-Nasrabadi M, Plonska-
phitic carbon nitride-based materials for photocatalytic antibacte- Brzezinska ME, Ahmadi F (2020) Introducing a novel nanocom-
rial application. Mater Sci Eng R 145:100610 posite consisting of nitrogen-doped carbon nano-onions and gold
16. Annamalai J, Murugan P, Ganapathy D, Nallaswamy D, Atchudan nanoparticles for the electrochemical sensor to measure acetami-
R, Arya S, Khosla A, Barathi S, Sundramoorthy AK (2022) Syn- nophen. J Electroanal Chem 871:114309
thesis of various dimensional metal organic frameworks (MOFs) 34. Niu X, Bo X, Guo L (2021) Ultrasensitive simultaneous voltam-
and their hybrid composites for emerging applications–a review. metric determination of 4-aminophenol and acetaminophen based
Chemosphere 298:134184 on bimetallic MOF-derived nitrogen-doped carbon coated CoNi
17. Kahkha MRR, Kaykhaii M, Sargazi G, Kahkha BR (2019) Deter- alloy. Anal Chim Acta 1145:37–45
mination of nicotine in saliva, urine and wastewater samples using 35. Lu X, Zhang F, Sun Y, Yu K, Guo W, Qu F (2021) A 2D/2D
tantalum metal organic framework pipette tip micro-solid phase NiCo-MOF/Ti3C2 heterostructure for the simultaneous detection
extraction. Anal Methods 11:6168–6175 of acetaminophen, dopamine and uric acid by differential pulse
18. Liu B, Jiang M, Zhu D, Zhang J, Wei G (2022) Metal-organic voltammetry. Dalton Trans 50:16593–16600
frameworks functionalized with nucleic acids and amino acids 36. Wu M, Wang L, Xu F, Ma G (2022) Preparation of Ni-MOF
for structure-and function-specific applications: a tutorial review. superstructure-reduced graphene oxide composite for enhanced
Chem Eng J 428:131118 electrochemical sensing of acetaminophen. Ionics 28:5571–5580
19. Hao F, Yan ZY, Yan XP (2022) Recent advances in research on 37. Yang Y, Li X, Gu Y, Lin H, Jie B, Zhang Q, Zhang X (2022)
the effect of physicochemical properties on the cytotoxicity of Adsorption property of fluoride in water by metal organic frame-
metal-organic frameworks. Small Sci 2:2200044 work: optimization of the process by response surface methodol-
20. Liu J-Q, Kumar A, Srivastava D, Pan Y, Dai Z, Zhang W, Liu Y, ogy technique. Surf Interfaces 28:101649
Qiu Y, Liu S (2022) Recent advances on bimetallic metal-organic 38. Jeyaseelan A, Viswanathan N (2021) Facile synthesis of tunable
frameworks (BMOFs): syntheses, applications and challenges. rare earth based metal organic frameworks for enhanced fluoride
New J Chem 46:13818–13837 retention. J Mol Liq 326:115163
21. Chen L, Wang H-F, Li C, Xu Q (2020) Bimetallic metal–organic 39. Cai D, Chen B, Huang Z, Zeng X, Xiao J, Zhou S-F, Zhan G
frameworks and their derivatives. Chem Sci 11:5369–5403 (2021) Metal oxide/CeO2 nanocomposites derived from Ce-ben-
22. Kumari A, Kaushal S, Singh PP (2021) Bimetallic metal organic zene tricarboxylate (Ce-BTC) adsorbing with metal acetylaceto-
frameworks heterogeneous catalysts: design, construction, and nate complexes for catalytic oxidation of carbon monoxide. RSC
applications. Mater Today Energy 20:100667 Adv 11:21057–21065
23. Zhang L, Deng S, Zhang Y, Peng Q, Li H, Wang P, Fu X, Lei 40. Farrag M (2021) In situ preparation of palladium nanoclusters
X, Qin A, Yu X (2020) Homotypic targeting delivery of siRNA in cerium metal-organic frameworks Ce-MOF-808, Ce-UiO-66
withartificial cancer cells. Adv. Healthc. Mater. 9(9):1900772 and Ce-BTC as nanoreactors for room temperature Suzuki cross-
24. Salama RS, Mannaa MA, Altass HM, Ibrahim AA, Khder AE-RS coupling reaction. Microporous Mesoporous Mater 312:110783
(2021) Palladium supported on mixed-metal–organic framework 41. Kibasomba PM, Dhlamini S, Maaza M, Liu C-P, Rashad MM,
(Co–Mn-MOF-74) for efficient catalytic oxidation of CO. RSC Rayan DA, Mwakikunga BW (2018) Strain and grain size of
Adv 11:4318–4326 ­TiO2 nanoparticles from TEM, Raman spectroscopy and XRD:
25. Tiwari A, Sagara PS, Varma V, Randhawa JK (2019) Bimetallic the revisiting of the Williamson-Hall plot method. Results Phys
metal organic frameworks as magnetically separable heterogene- 9:628–635
ous catalysts and photocatalytic dye degradation. ChemPlusChem 42. Rani N, Chahal S, Chauhan AS, Kumar P, Shukla R, Singh S
84:136–141 (2019) X-ray analysis of MgO nanoparticles by modified Scher-
26. Fan M, Yan J, Cui Q, Shang R, Zuo Q, Gong L, Zhang W (2023) er’s Williamson-Hall and size-strain method. Mater Today: Proc
Synthesis and peroxide activation mechanism of bimetallic MOF 12:543–548
for water contaminant degradation: a review. Molecules 28:3622 43. Nath D, Singh F, Das R (2020) X-ray diffraction analysis by
27. Kaushal S, Kaur G, Kaur J, Singh PP (2021) First transition series Williamson-Hall, Halder-Wagner and size-strain plot methods
metal–organic frameworks: synthesis, properties and applications. of CdSe nanoparticles-a comparative study. Mater Chem Phys
Mater Adv 2:7308–7335 239:122021
28. Singh S, Kaushal S, Kaur J, Kaur G, Mittal SK, Singh PP (2021) 44. Aly KA, Khalil N, Algamal Y, Saleem QM (2017) Estimation of
CaFu MOF as an efficient adsorbent for simultaneous removal lattice strain for zirconia nano-particles based on Williamson-Hall
analysis. Mater Chem Phys 193:182–188

13
1838 A. A. Moghadam et al.

45. Xia F, Kang S, Xue F, Bu X (2021) Simple reductive synthesis of Kongdian Formation, Cangdong Sag, Bohai Bay Basin. Front
a novel mixed-lanthanide metal–organic framework with excellent Earth Sci 9:760583
cycling ability as a binder-free supercapacitor electrode. Mater
Lett 282:128715 Publisher's Note Springer Nature remains neutral with regard to
46. Zhang X, Hou F, Li H, Yang Y, Wang Y, Liu N, Yang Y (2018) jurisdictional claims in published maps and institutional affiliations.
A strawsheave-like metal organic framework Ce-BTC derivative
containing high specific surface area for improving the catalytic Springer Nature or its licensor (e.g. a society or other partner) holds
activity of CO oxidation reaction. Microporous Mesoporous Mater exclusive rights to this article under a publishing agreement with the
259:211–219 author(s) or other rightsholder(s); author self-archiving of the accepted
47. Rahman M, Shafiullah AZ, Pal A, Islam M, Jahan I, Saha BB manuscript version of this article is solely governed by the terms of
(2021) Study on optimum IUPAC adsorption isotherm models such publishing agreement and applicable law.
employing sensitivity of parameters for rigorous adsorption sys-
tem performance evaluation. Energies 14:7478
48. Pan S, Zha M, Gao C, Qu J, Ding X (2021) Pore structure and
fractal characteristics of organic-rich lacustrine shales of the

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