NJC

View Article Online

PAPER View Journal | View Issue
Published on 14 March 2023. Downloaded by CHULALONGKORN UNIVERSITY on 10/15/2024 10:02:18 AM.

Understanding the activity of single atom

catalysts for CO2 reduction to C2 products:
Cite this: New J. Chem., 2023,
47, 7225 A high throughput computational screening†
Afshana Hassan and Manzoor Ahmad Dar *

The tunable electronic structure of the central metal atoms in single-atom catalysts (SACs) helps to
control the adsorption energy of reactants and different reaction intermediates involved in multistep
chemical processes. Although SACs have been recently proposed to be effective for electrochemical
CO2 reduction to C1 products such as HCOOH, CH3OH and CH4, their role in catalysing CO2 reduction
to C2 products involving more complex reaction pathways is largely unknown. Herein, by means of
systematic first-principles simulations, we thoroughly evaluate a total of 27 transition metal-based SACs
supported on a g-C2N monolayer for CO2 reduction to C2 products such as ethene and ethanol. Our
results demonstrate that the SACs reveal limiting potential values ranging from 1.50 to 2.70 V and are
capable of effectively suppressing the competitive hydrogen evolution reaction. The most effective
candidates capable of reducing CO2 to C2 products were found to be Cu@C2N, Cr@C2N, and Fe@C2N
exhibiting limiting potential values of 1.50, 2.23, and 2.27 V, respectively. We further find that the
Received 16th January 2023, catalytic activities of all the SACs can be correlated with the adsorption free energy of one of the
Accepted 13th March 2023 intermediate species (*COCH2O) making it a suitable descriptor for evaluating their CO2 reduction
DOI: 10.1039/d3nj00247k activity. Hence, this study provides key inputs regarding CO2 conversion to C2 products on SACs and is
expected to lead to further explorations for future design of SACs for the formation of multicarbon
rsc.li/njc products.

Introduction involves transfer of 2 electrons and is kinetically more feasible

has been the focus of electrocatalytic CO2 reduction.7 However,
CO2 reduction to valuable chemicals is highly appealing due to from an application standpoint, the conversion of CO2 to C2
its potential for mitigating the dependence of mankind on non- hydrocarbons is highly imperative because of the versatility
renewable fossil resources in a much greener manner.1–3 CO2 of C2 products in the chemical industry8–11 as well as their
as a member of the carbon pool is expected to have great higher economic value per unit mass compared with C1
potential for becoming a suitable feedstock for generating C1, counterparts.12,13 Also it is well known that the catalyst surface
C2 and C2+ hydrocarbons.4,5 Despite recent advancements, the and operating circumstances such as temperature, pressure,
poor product selectivity coupled with a competing hydrogen and CO2 concentration have a determining impact on the
evolution reaction (HER) makes the electrochemical CO2RR reaction pathways leading to the formation of C2 hydro-
highly challenging for practical applications on an industrial carbons.14 Electrocatalytic reduction of CO2 to C2 hydrocarbons
scale.6 These challenges necessitate a better understanding of holds great promise and is expected to bring down the energy
the CO2RR reaction mechanism as well as new design concepts requirements for the all-important step of C-C coupling with
for more effective electrocatalysis. Recently generation of the help of suitable catalysts in the presence of water using
C1 products such as formic acid and carbon dioxide, which renewable energy under ambient conditions.15–18
Despite holding great promise, the electrocatalytic conver-
Department of Chemistry, Islamic University of Science and Technology, sion of CO2 to C2 hydrocarbons still remains highly challenging
Kashmir 192122, India. E-mail: manzoor.dar@islamicuniversity.edu.in due to the non-availability of suitable catalysts19,20 which
† Electronic supplementary information (ESI) available: Reaction pathways for can catalyse C–C coupling under ordinary conditions in a cost
CO2 reduction to C2H4 and C2H5OH, adsorption free energies of CO2 reduction
effective manner. Thus, the design of new and out of the
intermediates on SACs supported on the g-C2N monolayer, the linear correlation
between adsorption free energy of intermediate species and that of *COCH2O and
box catalysts with suitable electronic structure and enhanced
predicted limiting potential values for Cr, Mn, Fe, Co, Cu, Tc, Rh, Pd, Re, Os and performance for CO2 reduction to C2 hydrocarbons is of
Ir-based SACs. See DOI: https://doi.org/10.1039/d3nj00247k paramount importance and occupies top priority among

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2023 New J. Chem., 2023, 47, 7225–7231 | 7225
 View Article Online

Paper NJC

researchers around the globe. Towards this direction transition

metal based catalysts have been rigorously explored and thus
far copper has been reported to be particularly active in the
synthesis of C2 compounds.21,22 Researchers have demon-
strated that carefully modified copper can be somewhat selec-
tive for C2 electroproduction; however, C1 and C3 species are
Published on 14 March 2023. Downloaded by CHULALONGKORN UNIVERSITY on 10/15/2024 10:02:18 AM.

still produced concurrently.21,23,24 Nilsson et al. revealed that

cubic nanostructured copper can considerably improve CO2
reduction selectivity to ethylene.24 Apart from experiments, the
mechanism of C2 product production on Cu surfaces has been
studied using density functional theory (DFT). In one investiga- Fig. 1 Representative sites for adsorption of transition metals on a 2  2
tion, researchers discovered that the Cu(100) surface is more g-C2N monolayer with a vacuum space of 20 Å along the z-axis.
likely to form a CO-CO couple than Cu(111) when two adsorbed
CO are present.25
EDIFFG values of 105 and 102 for energy and structure
Recently a new class of innovative catalysts known as single-
optimizations respectively. The SACs were modelled on a
atom catalysts (SACs) has gained popularity in catalysing a wide
2  2 C2N supercell with a vacuum space of 20 A1 along the
range of chemical reactions. In comparison to bulk metals,
z-direction to avoid the interaction between two periodic units
SACs dispersed on suitable supports possess unique electronic
as depicted in Fig. 1. Free energy diagrams were obtained using
structure, high activity and selectivity, and maximum atomic
the computational hydrogen electrode model41–43 where the
utilization.26–30 Owing to these reasons, many interesting
reaction free energy of a reaction step generating species B from
experimental and theoretical research works have surfaced
species A was calculated as
to better understand and screen the activity of single atom
catalysts for CO2 reduction to C1 products such as CO and DG = DE + DEZPE  TDS
HCOOH.9,10,31,32 Although SACs are widely used for CO2RR to
where DE, DEZPE and DS are the difference of the electronic
C1 products, the formation of multicarbon products on SACs is
energy, zero-point energy, and entropy, respectively, between
still a challenge and more work needs to be done in this
reactant A and product B. The zero-point energy and entropy
direction. Recently some studies have been carried out wherein
were estimated from vibrational frequency calculations of
it has been revealed that Cu-based SACs can be utilized for the
adsorbed intermediates using the Vaspkit code44 at room
reduction of CO2 to C2 products.33–35 However due to the lack of
temperature (298.15 K). The solvent calculations were done
direct experimental probes and the complexity of the reaction
using the VASPsol package, in which a solute is placed in the
conditions, the true nature of these Cu-based catalysts is
cavity surrounded by a continuum dielectric description of the
still inconclusive. Moreover, beyond Cu-based single atoms,
solvent.45
not many other studies have been carried out to explore the
role of SACs to catalyse CO2 conversion to C2 products. This
necessitates further efforts to screen single atoms for CO2
reduction to C2 products to gain better understanding and
Results and discussion
design new catalysts with improved activity and selectivity. We begin the discussion on the stability of the SACs adsorbed
Towards this direction in the current work, we have screened on the C2N monolayer by evaluating their binding energies with
27 different transition metal-based SACs anchored on g-C2N to the monolayer as depicted in Fig. 1 and comparing it with the
understand CO2 reduction to C2 products such as ethylene and bulk cohesive energy. The calculated values of binding energy
ethanol using standard first principle simulations. for the different SACs with the C2N monolayer and the bulk
cohesive energies are shown in Table 1. It can be seen from
Table 1 that the computed binding energy values for the SACs
Computational details
Table 1 Binding energy values of TM@C2N (ETM). EBulk represents the
The Vienna ab initio simulation package (VASP)36,37 was used
experimental bulk cohesive energies of the transition metals
to carry out the spin-polarized density functional theory calcu-
lations and the electron interactions and electron–ion interac- TM ETM EBulk TM ETM EBulk TM ETM EBulk
(3d) (eV) (eV) (4d) (eV) (eV) (5d) (eV) (eV)
tions were described by the Perdew–Burke–Ernzerhof (PBE)38
exchange-correlation functional within the generalized gradi- Sc 7.75 3.90 Y 8.95 4.37 La 11.06 4.47
ent approximation and projector augmented wave (PAW) Ti 11.73 4.85 Zr 9.02 6.25 Hf 9.12 6.44
V 9.28 5.31 Nb 7.53 7.57 Ta 8.37 8.10
method, respectively.39 For the treatment of possible van der Cr 7.16 4.10 Mo 5.54 6.82 W 6.57 8.90
Waals (vdW) interactions between different adsorbed species Mn 4.55 2.92 Tc 5.67 6.85 Re 5.23 8.03
and catalysts, Grimme’s semiempirical DFT-D3 scheme of Fe 4.70 4.28 Ru 5.72 6.74 Os 5.99 8.17
Co 5.23 4.39 Rh 5.40 5.75 Ir 5.84 6.94
dispersion correction was employed.40 A kinetic energy cutoff Ni 4.69 4.44 Pd 3.22 3.89 Pt 4.44 5.84
of 500 eV was used for the plane-wave basis with EDIFF and Cu 3.41 3.49 Ag 3.11 2.95 Au 2.60 3.81

7226 | New J. Chem., 2023, 47, 7225–7231 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2023
 View Article Online

NJC Paper
Published on 14 March 2023. Downloaded by CHULALONGKORN UNIVERSITY on 10/15/2024 10:02:18 AM.

Fig. 2 Calculated adsorption free energy values of the first protonation step (*COOH) in the CO2 reduction and H atom on the (a) 3d, (b) 4d and
(c) 5d TM@C2N catalysts.

are either comparable or greater than the experimental bulk

cohesive energies46 for all the transition metal atoms. The
significantly large binding energy values compared to bulk
cohesive energy indicate the enhanced stability of SACs
adsorbed on the C2N monolayer.
Since the hydrogen evolution reaction (HER) is the main
competing reaction in the electrocatalytic reduction of CO2 as
the proton-electron pair can easily cover the SACs,19 a preli-
minary screening based on G(*H) and G(*COOH) values was
performed on all the SACs, as depicted in Fig. 2. The results
reveal that all 27 candidates favour hydrogenation of CO2
(forming *COOH) over that of H adsorption, showing a higher
degree of selectivity for the CO2RR compared to the HER.
Having screened all the 27 transition metal-based SACs, we
next proceeded for CO2 reduction on all the screened catalysts

Fig. 3 Computed limiting potentials for the CO2RR on different transition Fig. 4 Proposed reaction pathway for CO2 reduction to C2 products
metal-based SACs. (C2H4 and C2H5OH) on g-C2N based SACs.

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2023 New J. Chem., 2023, 47, 7225–7231 | 7227
 View Article Online

Paper NJC

to C2 products (ethene and ethanol) as per the reaction scheme The computed free energy pathways for all the catalysts are
shown in Fig. 4. The above reaction mechanism is already well given in Fig. 5 and Fig. S1 and S2 (ESI†) with the limiting
documented in the literature47 for CO reduction to C2 products on potentials of the CO2RR towards the C2 products (C2H4 and
metal surfaces. Furthermore, it is known that CO2 is first trans- C2H5OH) for all SACs summarized in Fig. 3. Among the 27
formed to CO before being reduced further and leads to the same catalysts, 11 catalysts namely M@C2N (M = Cr, Mn, Fe, Co, Cu,
product distribution as CO2.17,48 As shown in the figure, one of the Tc, Rh, Pd, Re, Os and Ir) were found to reduce CO2 to C2H4 and
Published on 14 March 2023. Downloaded by CHULALONGKORN UNIVERSITY on 10/15/2024 10:02:18 AM.

routes involves *CHO or *COH intermediates, which then combine C2H5OH at low limiting potentials. Furthermore, Cu, Cr and
with an incoming *CO molecule before the formation of the final Fe-based SACs exhibit the lowest limiting potential values of
C2 products. The second route involves the coupling of a *CO 1.50, 2.23, and 2.27 V among the 27 screened catalysts as
molecule with an adsorbed *CO species generated from CO2 revealed by the reaction free energy pathways depicted in Fig. 5.
hydrogenation, resulting in the formation of *COCO species, It can be seen in the free energy pathways that *COCO
which undergo subsequent hydrogenation to form C2 products. formation is thermodynamically favourable whereas both *CHO

Fig. 5 The reaction pathways for CO2 reduction to C2H4 and C2H5OH on (a) Cr@C2N, (b) Fe@C2N, and (c) Cu@C2N. The most favourable pathways are
highlighted in blue colour.

7228 | New J. Chem., 2023, 47, 7225–7231 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2023
 View Article Online

NJC Paper

and *COH are formed with some energy requirement in the case
of all eleven catalysts (Fig. 5 and Fig. S1, ESI†). Subsequently, with
the adsorption of CO on *CHO, *COH leads to the formation of
*COCHO and *COCOH, respectively, whereas both *COCHO or
*COCOH can be formed by the hydrogenation of *COCO. It is
worth noting that the coupling step i.e., formation of *COCO,
Published on 14 March 2023. Downloaded by CHULALONGKORN UNIVERSITY on 10/15/2024 10:02:18 AM.

*COCHO or *COCOH from *CO is favoured in all eleven catalysts,

which is a crucial step for the formation of C2 products. It can
be seen in the free energy pathways that Cr@C2N, Mn@C2N,
Fe@C2N and Co@C2N proceed towards ethylene and ethanol
formation either through *COH or *COCO with the fifth step
of hydrogenation (*COCOH - *CCO) being the most energy
demanding step. In the case of Cu@C2N and Pd@C2N, ethylene
and ethanol are formed as the final products through the hydro-
genation of either *COH or *COCO. As can be seen from the
reaction pathways of Cu@C2N and Pd@C2N, the rate determining Fig. 6 Free energy change for reaction steps, based on linear correlation
step is the 6th hydrogenation step (*COHCOH - *CCOH). between adsorption free energy of intermediates and DGðCOCH2OÞ .
Furthermore, in the case of Tc@C2N, Rh@C2N, and Ir@C2N,
the rate determining step comes out to be the 8th step of
hydrogenation i.e., *CHOHCH2O - *CHCH2O for the formation intermediates namely *CO, *CHO, *H2O and *C2H5OH is weakly
of both ethylene and ethanol whereas, only ethylene is formed as correlated with DGðCOCH2 OÞ . The nearly linear correlation
a favourable product in the case of Re@C2N and Os@C2N with between the adsorption free energy of the different intermediate
*COOH - *CO and *COCO - *COCOH as the rate limiting species and DGðCOCH2 OÞ allows direct prediction of the related
steps, respectively. The limiting potential values for Cr@C2N, activity of the studied SACs. Based on the linear correlations
Mn@C2N, Fe@C2N, Co@C2N, Cu@C2N, Tc@C2N, Rh@C2N, (Tables S1 and S2, ESI†), the reaction free energy of each step
Pd@C2N, Re@C2N, Os@C2N and Ir@C2N are 2.23, 2.35, can be written as a linear function of DGðCOCH2 OÞ by plotting the
2.27, 2.60, 1.50, 2.70, 2.61, 2.51, 2.39, 2.46, and reaction free energy of each step for all the screened catalysts
2.55 V, respectively. These results show that Cu@C2N, Cr@C2N (Cr@C2N, Mn@C2N, Fe@C2N, Co@C2N, Cu@C2N, Tc@C2N,
and Fe@C2N are the most suitable single-atom catalysts for the Rh@C2N, Pd@C2N, Re@C2N, Os@C2N and Ir@C2N) against
CO2 reduction to C2 products exhibiting limiting potential values DGðCOCH2 OÞ . It can be seen from Fig. S6 (ESI†) that the highest
of 1.50, 2.23 and 2.27 V, respectively, for CO2 reduction to C2 values of the free energy of the intermediate steps lie on the two
products. Moreover, the inclusion of the solvent effect has a lines corresponding to the reaction steps (*CO - *COOH and
negligible impact on the limiting potential values with 1.48, *CHCH2O - *CHOHCH2O) as depicted more clearly in Fig. 6
2.28 and 2.20 V Cu@C2N, Fe@C2N, and Cr@C2N respectively, resulting in an inverted volcano. Hence, the limiting potential
which is in line with earlier reported results.32,49,50 We also values can be predicted by using these highest values of the free
computed the kinetic barriers for the PDS using the climbing energy (Table S3, ESI†) lying at the top of the plot. Furthermore,
image nudged elastic band calculations, as shown in Fig. S3 we plotted the values of the limiting potential (shown by solid
(ESI†). Activation barriers of 1.02, 1.34 and 0.86 eV are noted for cyan triangles) of all the catalysts obtained directly from the
Cr@C2N, Fe@C2N, and Cu@C2N, respectively. To confirm the reaction free energy pathways in Fig. 6 to confirm the reliability
thermal stability of the most suitable catalysts, AIMD simulations of the model. Interestingly it turned out that the obtained values
using the CP2K package were carried out at 600 K using a Nose– of limiting potential are in reasonable agreement with the limiting
Hoover thermostat.51 AIMD results reveal that all the atoms in potential values predicted by the model (see Table S3, ESI†). These
Cu@C2N, Cr@C2N and Fe@C2N vibrate about their equilibrium findings indicate that the reaction free energy values obtained by
positions with no major structural distortion (Fig. S4, ESI†). the linear correlation between the adsorption free energy of the
Finally based on the simulated results, we look to develop a intermediates and DGðCOCH2 OÞ can be used as a reasonable guess
correlation between the adsorption free energies of different to predict the limiting potentials of the SACs and related catalysts
reaction intermediates involved in CO2 reduction to C2 products. for CO2 reduction to C2 products, thereby making DGðCOCH2 OÞ an
The Sabatier principle states that an interaction between a catalyst appropriate descriptor for assessing the activity of the CO2RR to
and a key intermediate species should not be either too strong or C2 products.
too weak to permit active catalysis.46 Consequently, there is a close
relationship between the reaction mechanisms and the adsorp-
tion free energy of the intermediates. Hence a correlation between Conclusions
the adsorption free energies might provide valuable information.
As shown in Fig. S5 (ESI†), the adsorption free energies of 21 In conclusion, we evaluated the catalytic activity of 27 different
intermediates are strongly correlated with the adsorption free transition metal atom-based SACs supported on a g-C2N mono-
energy of *COCH2O, whereas the adsorption free energy of four layer for CO2 reduction to C2 products by means of first

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2023 New J. Chem., 2023, 47, 7225–7231 | 7229
 View Article Online

Paper NJC

principles simulations. According to our thorough analysis, we 9 Y. Cheng, S. Yang, S. P. Jiang and S. Wang, Small Methods,
find that Cu@C2N, Cr@C2N, and Fe@C2N are the most active 2019, 3, 1800440.
electrocatalysts for the conversion of CO2 towards the C2 10 L. Lin, G. Wang, X. Bao and C. Yan, Chin. J. Catal., 2018, 40,
products C2H4 and C2H5OH with limiting potential values of 23–37.
1.50, 2.23, and 2.27 V, respectively. The SACs can suppress 11 Y. Cheng, S. Zhao, B. Johannessen, J. P. Veder, M. Saunders,
the competitive hydrogen evolution reaction thereby making M. R. Rowles, M. Cheng, C. Liu, M. F. Chisholm, R. De
Published on 14 March 2023. Downloaded by CHULALONGKORN UNIVERSITY on 10/15/2024 10:02:18 AM.

CO2 reduction highly selective on these catalysts. In addition Marco, H. M. Cheng, S. Z. Yang and S. P. Jiang, Adv. Mater.,
to this, we find that the adsorption free energy of different 2018, 30, e1706287.
reaction intermediates can be linearly correlated with DGðCOCH2 OÞ 12 J. Hill, E. Nelson, D. Tilman, S. Polasky and D. Tiffany, Proc.
which helps in forecasting the activity of SACs. Natl. Acad. Sci., 2006, 103, 11206–11210.
13 A. E. Farrell, R. J. Plevin, B. T. Turner, A. D. Jones, M. O’Hare
and D. M. Kammen, Science, 2006, 311, 506–508.
Author contributions 14 Y. Zheng, A. Vasileff, X. Zhou, Y. Jiao, M. Jaroniec and S.-
Z. Qiao, J. Am. Chem. Soc., 2019, 141, 7646–7659.
A. H. performed the theoretical calculations and analysed the
15 D. U. Nielsen, X.-M. Hu, K. Daasbjerg and T. Skrydstrup,
results. M. A. D. conceptualized the study and carried out
Nat. Catal., 2018, 1, 244–254.
advising. Both the authors contributed to the preparation of
16 P. De Luna, C. Hahn, D. Higgins, S. A. Jaffer, T. F. Jaramillo
the manuscript.
and E. H. Sargent, Science, 2019, 364, 1–9.
17 K. J. P. Schouten, Y. Kwon, C. J. M. van der Ham, Z. Qin and
M. T. M. Koper, Chem. Sci., 2011, 2, 1902–1909.
Conflicts of interest
18 D. Gao, R. M. Arán-Ais, H. S. Jeon and B. Roldan Cuenya,
The authors declare no conflict of interest. Nat. Catal., 2019, 2, 198–210.
19 J. Qiao, Y. Liu, F. Hong and J. Zhang, Chem. Soc. Rev., 2014,
43, 631–675.
Acknowledgements 20 S. Nitopi, E. Bertheussen, S. B. Scott, X. Liu, A. K. Engstfeld,
S. Horch, B. Seger, I. E. L. Stephens, K. Chan, C. Hahn,
A. H. acknowledges the fellowship from SERB grant [SRG/2020/
J. K. Nørskov, T. F. Jaramillo and I. Chorkendorff, Chem.
000654]. M. A. D. acknowledges Start-up research grants from
Rev., 2019, 119, 7610–7672.
SERB [SRG/2020/000654], India for financial support towards
21 R. Kortlever, I. Peters, C. Balemans, R. Kas, Y. Kwon,
the completion of this work. We acknowledge National Super-
G. Mul and M. T. M. Koper, Chem. Commun., 2016, 52,
computing Mission (NSM) for providing computing resources
10229–10232.
of ‘PARAM Smriti’ at NABI, Mohali, which is implemented by
22 Y. Liu, S. Chen, X. Quan and H. Yu, J. Am. Chem. Soc., 2015,
C-DAC and supported by the Ministry of Electronics and
137, 11631–11636.
Information Technology (MeitY) and Department of Science
23 H. Yano, T. Tanaka, M. Nakayama and K. Ogura, J. Electroanal.
and Technology (DST), Government of India.
Chem., 2004, 565, 287–293.
24 A. Loiudice, P. Lobaccaro, E. A. Kamali, T. Thao, B. H.
References Huang, J. W. Ager and R. Buonsanti, Angew. Chem., Int.
Ed., 2016, 55, 5789–5792.
1 M. Aresta, A. Dibenedetto and A. Angelini, Chem. Rev., 2014, 25 J. H. Montoya, C. Shi, K. Chan and J. K. Nørskov, J. Phys.
114, 1709–1742. Chem. Lett., 2015, 6, 2032–2037.
2 G. Centi, E. A. Quadrelli and S. Perathoner, Energy Environ. 26 Z. W. Chen, L. X. Chen, C. C. Yang and Q. Jiang, J. Mater.
Sci., 2013, 6, 1711–1731. Chem. A, 2019, 7, 3492–3515.
3 G. A. Olah, G. K. S. Prakash and A. Goeppert, J. Am. Chem. 27 Y. Zhu, J. Sokolowski, X. Song, Y. He, Y. Mei and G. Wu, Adv.
Soc., 2011, 133, 12881–12898. Energy Mater., 2020, 10, 1902844.
4 R. Francke, B. Schille and M. Roemelt, Chem. Rev., 2018, 28 A. Maibam, S. Krishnamurty and M. Ahmad Dar, Mater.
118, 4631–4701. Adv., 2022, 3, 592–598.
5 D. D. Zhu, J. L. Liu and S. Z. Qiao, Adv. Mater., 2016, 28, 29 S. S. Deshpande, M. D. Deshpande, T. Hussain and R. Ahuja,
3423–3452. J. CO2 Util., 2020, 35, 1–13.
6 Y. Hori, H. Wakebe, T. Tsukamoto and O. Koga, Electrochim. 30 A. Rasool, I. Anis, M. Dixit, A. Maibam, A. Hassan,
Acta, 1994, 39, 1833–1839. S. Krishnamurty and M. A. Dar, Catal. Sci. Technol., 2022,
7 B. C. Marepally, C. Ampelli, C. Genovese, T. Saboo, 12, 310–319.
S. Perathoner, F. M. Wisser, L. Veyre, J. Canivet, E. A. 31 A. S. Varela, W. Ju and P. Strasser, Adv. Energy Mater., 2018,
Quadrelli and G. Centi, ChemSusChem, 2017, 10, 4442–4446. 8, 1703614.
8 O. S. Bushuyev, P. De Luna, C. T. Dinh, L. Tao, G. Saur, J. van 32 A. Hassan, I. Anis, S. Shafi, A. Assad, A. Rasool, R. Khanam,
de Lagemaat, S. O. Kelley and E. H. Sargent, Joule, 2018, 2, G. A. Bhat, S. Krishnamurty and M. A. Dar, ACS Appl. Nano
825–832. Mater., 2022, 5, 15409–15417.

7230 | New J. Chem., 2023, 47, 7225–7231 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2023
 View Article Online

NJC Paper

33 D. Karapinar, N. T. Huan, N. Ranjbar Sahraie, J. Li, 42 A. A. Peterson, F. Abild-Pedersen, F. Studt, J. Rossmeisl and
D. Wakerley, N. Touati, S. Zanna, D. Taverna, L. H. Galvão J. K. Nørskov, Energy Environ. Sci., 2010, 3, 1311–1315.
Tizei, A. Zitolo, F. Jaouen, V. Mougel and M. Fontecave, 43 J. Rossmeisl, A. Logadottir and J. K. Nørskov, Chem. Phys.,
Angew. Chem., Int. Ed., 2019, 58, 15098–15103. 2005, 319, 178–184.
34 H. Guzmán, N. Russo and S. Hernández, Green Chem., 2021, 44 V. Wang, N. Xu, J.-C. Liu, G. Tang and W.-T. Geng, Comput.
23, 1896–1920. Phys. Commun., 2021, 267, 108033.
Published on 14 March 2023. Downloaded by CHULALONGKORN UNIVERSITY on 10/15/2024 10:02:18 AM.

35 K. Zhao, X. Nie, H. Wang, S. Chen, X. Quan, H. Yu, W. Choi, 45 K. Mathew, R. Sundararaman, K. Letchworth-Weaver, T. A.
G. Zhang, B. Kim and J. G. Chen, Nat. Commun., 2020, Arias and R. G. Hennig, J. Chem. Phys., 2014, 140, 084106.
11, 2455. 46 P. Janthon, S. Luo, S. M. Kozlov, F. Viñes, J. Limtrakul,
36 G. Kresse and J. Furthmüller, Phys. Rev. B: Condens. Matter D. G. Truhlar and F. Illas, J. Chem. Theory Comput., 2014, 10,
Mater. Phys., 1996, 54, 11169–11186. 3832–3839.
37 J. Hafner, J. Comput. Chem., 2008, 29, 2044–2078. 47 A. J. Garza, A. T. Bell and M. Head-Gordon, ACS Catal., 2018,
38 J. P. Perdew, K. Burke and M. Ernzerhof, Phys. Rev. Lett., 8, 1490–1499.
1996, 77, 3865–3868. 48 Y. Hori, R. Takahashi, Y. Yoshinami and A. Murata, J. Phys.
39 P. E. Blöchl, Phys. Rev. B: Condens. Matter Mater. Phys., 1994, Chem. B, 1997, 101, 7075–7081.
50, 17953–17979. 49 Q. Jiang, Y. Meng, K. Li, Y. Wang and Z. Wu, Appl. Surf. Sci.,
40 S. Grimme, J. Antony, S. Ehrlich and H. Krieg, J. Chem. Phys., 2021, 547, 149208.
2010, 132, 154104. 50 J. H. Montoya, C. Tsai, A. Vojvodic and J. K. Nørskov,
41 J. K. Nørskov, J. Rossmeisl, A. Logadottir, L. Lindqvist, J. R. ChemSusChem, 2015, 8, 2180–2186.
Kitchin, T. Bligaard and H. Jónsson, J. Phys. Chem. B, 2004, 51 J. Hutter, M. Iannuzzi, F. Schiffmann and J. VandeVondele,
108, 17886–17892. WIREs Comput. Mol. Sci., 2014, 4, 15–25.

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2023 New J. Chem., 2023, 47, 7225–7231 | 7231