First-principles Study on Oxygen Evolution Reaction Activity of CoPS3 Quantum Dots Edge States Modified with Oxygen

doi:10.15541/jim20250092

Abstract

Abstract:

Two-dimensional CoPS₃ electrocatalyst for water splitting suffers from scarcity of in-plane metal active sites, resulting in slow kinetics for oxygen evolution reaction (OER) at anode, thereby limiting overall efficiency of hydrogen production via water splitting. To address this issue, this study proposes a new strategy to enhance the catalytic activity through synergistic effects of quantum confinements and edge chemical modification. Initially, two typical CoPS₃ quantum dots (CoPS₃-QDs) structures with high edge-site densities were constructed. Through binding and bond energy calculations, structure of thermodynamically stable CoPS₃-QDs1 was identified, with its edge Co2 site exhibiting the best OER activity among other edge sites (Gibbs free energy change for the rate-determining step, ΔG at 1.68 eV). Subsequently, oxygen modification was introduced at Co2 site of the CoPS₃-QDs1 and its neighboring sulfur atoms, obtaining five O-CoPS₃-QDs models. Theoretical calculations revealed that the M4 model (with O modification at the S3 site) had an overpotential (η^OER) of only 0.32 V, which was 29% lower than that of the unmodified system but significantly better than that of the noble metal catalyst RuO₂ reported in the literature. Partial density of states analysis further revealed that O modification optimized charge redistribution around the Co sites, enabling moderate adsorptions of oxygen intermediates (*OH, *O, *OOH). This study elucidates the crucial role of edge-site modification of quantum dots in regulating electronic structure and reaction kinetics, providing a theoretical basis for designing efficient and low-cost OER electrocatalysts.

Key words: CoPS₃, quantum dot, oxygen evolution reaction, edge state

CLC Number:

TQ151

HU Xuemin, ZHANG Xingjian, JIANG Zhihao, HUANG Liwen, DING Kaining, ZHANG Shengli. First-principles Study on Oxygen Evolution Reaction Activity of CoPS₃ Quantum Dots Edge States Modified with Oxygen[J]. Journal of Inorganic Materials, 2025, 40(11): 1229-1236.

Figures/Tables 11

Fig. 1 Monolayer crystal structure model and quantum dots model of CoPS3 (a) Top and (b) side views of the monolayer CoPS3 structure model; (c, d) Top views of (c) CoPS3-QDs1 and (d) CoPS3-QDs2; Red dashed line in (a) indicating unit cell of CoPS3

Fig. 2 Optimized structure model and electronic property data of CoPS3-QDs1 (a) Top view of the optimized CoPS3-QDs1 structure model, where S1-S4, Co1, and Co2 represent six inequivalent edge atomic positions obtained from Mulliken charge calculations; (b) Charge density difference map of CoPS3-QDs1, where blue regions indicate electron accumulation and green regions indicate electron depletion, with isovalue=0.048 e/Å3; (c) Orbital-resolved partial density of states (PDOS) and (d) atom-resolved PDOS of CoPS3-QDs1. Colorful figures are available on website

Fig. 3 Step diagrams of Gibbs free energy for the OER at six adsorption sites of CoPS3-QDs1 and schematic illustrations of the adsorbed intermediate models (a) S1 site; (b) S2 site; (c) S3 site; (d) S4 site; (e) Co1 site; (f) Co2 site

Fig. 4 Structural models of O modification at the Co2 site of CoPS3-QDs1 and its surrounding four inequivalent S atoms (a) Distribution of Co2 site and its surrounding four S atomic sites; (b) Model M1 with O modification at the Co2 site; (c) Model M2 with O modification at the S1 site; (d) Model M3 with O modification at the S2 site; (e) Model M4 with O modification at the S3 site; (f) Model M5 with O modification at the S4 site. Colorful figures are available on website

Fig. 5 OER activity comparisons of M1-M5 models with O modification (a-e) Gibbs free energy diagrams for OER on (a) M1, (b) M2, (c) M3, (d) M4, and (e) M5 models with O modification; (f) Comparisons of the Gibbs free energy differences for the four electron transfer steps in the OER process for M1-M5 models. Colorful figures are available on website

Fig. 6 Comparison of density of states for M4 model before and after adsorption of OOH (a) Total PDOS and (b) atom-resolved PDOS of M4 model; (c) Total PDOS and (d) atom-resolved PDOS of M4 model after adsorbing *OOH. Colorful figures are available on website

Fig. S1 Optimized geometrical structure model of CoPS3-QDs1

Table S1 Fractional coordinates of each atom in the optimized geometrical structure model of CoPS3-QDs1

No.	Fractional coordinates
No.	X	Y	Z
Co1a	-0.251	0.002	-0.005
Co1b	0.275	0.002	-0.005
Co2a	-0.128	0.266	0.015
Co2b	0.152	0.266	0.015
Co2c	-0.128	-0.263	-0.026
Co2d	0.152	-0.263	-0.026
S1a	-0.239	0.167	-0.175
S1b	0.263	0.167	-0.175
S1c	-0.238	-0.164	0.165
S1d	0.262	-0.164	0.165
S2a	-0.315	0.187	0.137
S2b	0.339	0.187	0.137
S2c	-0.316	-0.184	-0.147
S2d	0.340	-0.184	-0.147
S3a	0.012	0.374	0.185
S3b	0.012	-0.369	-0.197
S4a	0.012	0.394	-0.130
S4b	0.012	-0.392	0.119
P1	0.012	0.070	0.084
P2	0.012	-0.066	-0.094

Fig. S2 Schematic structure models of six active sites (S1-S4, Co1 and Co2) of CoPS3-QDs1 adsorbing three oxygen intermediates (*OOH, *OH, and *O), illustrated using site S1 and Co2 as example

Fig. S3 Optimized structural models and charge density difference maps of O modification at the Co2 site of CoPS3-QDs1 and its surrounding four inequivalent S atoms, where blue regions indicate electron accumulation and green regions indicate electron depletion, with isovalue=0.2 e/Å3

Fig. S4 Schematic diagrams of the Co2 sites in the M1-M5 models for the adsorption of *OOH, *OH, and *O oxygen intermediates

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First-principles Study on Oxygen Evolution Reaction Activity of CoPS₃ Quantum Dots Edge States Modified with Oxygen

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