氧修饰的CoPS3量子点边缘态析氧活性的第一性原理研究

doi:10.15541/jim20250092

无机材料学报 ›› 2025, Vol. 40 ›› Issue (11): 1229-1236.DOI: 10.15541/jim20250092

氧修饰的CoPS₃量子点边缘态析氧活性的第一性原理研究

胡学敏¹^,²(), 张行健¹, 蒋志豪¹, 黄丽雯¹, 丁开宁³, 张胜利²()

1.金陵科技学院材料工程学院, 南京 211169
2.南京理工大学材料科学与工程学院, 南京 210094
3.福州大学化学学院, 福州 350108

收稿日期:2025-03-03 修回日期:2025-05-18 出版日期:2025-11-20 网络出版日期:2025-06-03
通讯作者: 张胜利, 教授. E-mail: zhangslvip@njust.edu.cn
作者简介:胡学敏(1986-), 女, 博士. E-mail: huxm@jit.edu.cn
基金资助:
国家自然科学基金(52202247);中国博士后科学基金(2024M764215);江苏省大学生创新训练项目(202413573104Y);金陵科技学院科教融合项目(2024KJRH35);金陵科技学院科研启动项目(JIT-B-202120);金陵科技学院孵化项目(jit-fhxm-202115)

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

HU Xuemin¹^,²(), ZHANG Xingjian¹, JIANG Zhihao¹, HUANG Liwen¹, DING Kaining³, ZHANG Shengli²()

1. School of Material Engineering, Jinling Institute of Technology, Nanjing 211169, China
2. School of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094, China
3. College of Chemistry, Fuzhou University, Fuzhou 350108, China

Received:2025-03-03 Revised:2025-05-18 Published:2025-11-20 Online:2025-06-03
Contact: ZHANG Shengli, professor. E-mail: zhangslvip@njust.edu.cn
About author:HU Xuemin (1986-), female, PhD. E-mail: huxm@jit.edu.cn
Supported by:
National Natural Science Foundation of China(52202247);China Postdoctoral Science Foundation(2024M764215);Jiangsu Province College Student Innovation and Entrepreneurship Training Program Project(202413573104Y);Science and Education Integration Project of Jinling Institute of Technology(2024KJRH35);PhD Scientific Research Startup Foundation of the Jinling Institute of Technology(JIT-B-202120);Scientific Research Fund Incubation Project of Jinling Institute of Technology(jit-fhxm-202115)

摘要/Abstract

摘要：

二维CoPS₃电催化剂面内金属活性位点稀缺, 用于阳极析氧反应(OER)的动力学过程缓慢, 这限制了整体电解水制氢的效率。针对这一问题, 本研究提出通过量子限域效应与边缘化学修饰协同提升催化活性的新策略。首先构建了两种典型的具有高边缘位点密度的CoPS₃量子点(CoPS₃-QDs)结构模型, 通过结合能和键能计算筛选出热力学稳定的结构(CoPS₃-QDs1), 其边缘Co2位点较其它边缘位点展现出最优OER活性(速率决定步骤的吉布斯自由能ΔG=1.68 eV)。进一步在CoPS₃-QDs1的Co2位点及邻近硫原子引入氧(O)修饰, 构建五种O-CoPS₃-QDs模型。理论计算表明, M4模型(O修饰于S3位点)的过电位(η^OER)仅为0.32 V, 较未修饰体系降低29%, 且显著优于文献报道的贵金属RuO₂催化剂。局域态密度分析进一步揭示, O修饰诱导Co位点附近的电荷重新分布, 可以适度吸附氧中间体(*OH、*O、*OOH)。本研究阐明了量子点边缘态修饰在调控电子结构与反应动力学中的关键作用, 为设计高效、低成本的OER电催化剂提供了理论依据。

关键词: CoPS₃, 量子点, 析氧反应, 边缘态

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

中图分类号:

TQ151

胡学敏, 张行健, 蒋志豪, 黄丽雯, 丁开宁, 张胜利. 氧修饰的CoPS₃量子点边缘态析氧活性的第一性原理研究[J]. 无机材料学报, 2025, 40(11): 1229-1236.

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.

图/表 11

图1 CoPS3的单层晶体结构模型和量子点结构模型

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

图2 几何优化后CoPS3-QDs1的结构模型和电子性质数据

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

图3 CoPS3-QDs1六种吸附位点的OER吉布斯自由能台阶图及各吸附中间体模型示意图

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

图4 O修饰CoPS3-QDs1 Co2位点及其周边四个不等价S原子的结构模型

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

图5 O修饰得到的M1~M5模型的OER活性对比

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

图6 M4模型吸附OOH中间体前、后的态密度图对比

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

图S1 几何优化后CoPS3-QDs1的结构模型

Fig. S1 Optimized geometrical structure model of CoPS3-QDs1

表S1 几何优化后CoPS3-QDs1各原子空间分布的分数坐标

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

图S2 CoPS3-QDs1的六个活性位点(S1~S4、Co1和Co2)上分别吸附了*OOH、*OH和*O三个氧中间体的结构模型示意图，分别以(a)S1和(b)Co2位点为例

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

图S3 几何优化后O修饰CoPS3-QDs1的Co2位点及其周边四个不等价S原子的结构模型和差分电荷密度分布，其中蓝色区域表示电子聚集，绿色区域表示电子损耗isovalue=0.2 e/Å3

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

图S4 吸附*OOH、*OH和*O三个氧中间体的M1~M5模型的Co2位点示意图

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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氧修饰的CoPS₃量子点边缘态析氧活性的第一性原理研究

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

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