无定形CoxHyPO4复合NiCo2S4核壳结构设计及其电催化析氧性能

蔡晓燕; 陈自豪; 毛梁

无定形Co_xH_yPO₄复合NiCo₂S₄核壳结构设计及其电催化析氧性能

中国矿业大学　材料与物理学院, 徐州 221116

基金项目: 国家自然科学基金 (22309204, 22209203)；博士后科学基金(2023M733742)；中国矿业大学材料科学与工程学科引导基金(CUMTMS202202, CUMTMS202207)

详细信息

通讯作者:
蔡晓燕，博士，副教授，硕士生导师，研究方向为光/电功能材料　E-mail: xycai@cumt.edu.cn

中图分类号: TB332
计量
- 文章访问数: 24
- HTML全文浏览量: 17
- 被引次数: 0
出版历程
- 收稿日期: 2024-05-07
- 修回日期: 2024-07-03
- 录用日期: 2024-07-05
- 网络出版日期: 2024-07-24

Core-shell structured Co_xH_yPO₄/NiCo₂S₄ composites towards electrocatalytic oxygen evolution

School of Materials Science and Physics, China University of Mining and Technology, Xuzhou 221116

Funds: National Natural Science Foundation of China (No. 22309204 and 22209203); China Postdoctoral Science Foundation (No. 2023M733742); Material Science and Engineering Discipline Guidance Fund of China University of Mining and Technology (No. CUMTMS202202 and CUMTMS202207)

摘要

摘要: 探索具有优异活性和稳定性的非贵金属析氧反应(OER)电催化剂是电解水制氢的关键。本文采用光还原沉积方法将无定形的非晶物质磷酸氢钴(Co_xH_yPO₄，简称Co-Pi)沉积在多孔NiCo₂S₄(NCS)蛋黄-蛋壳微球表面，成功制备出具有核壳结构的Co-Pi/NCS复合材料。密度泛函理论(DFT)计算与实验研究相结合，探究Co-Pi的引入对NCS电子结构和电催化性能的影响。异质界面的形成以及化学键的重构，可以提升Co-Pi/NCS的电导率，调节催化剂与反应中间体之间的电荷转移，从而改变吸附强度和反应的吉布斯自由能，最终优化OER催化活性。因此，Co-Pi/NCS表现出良好的催化活性和耐久性，在10 mA·cm⁻²电流密度下的过电位仅为335 mV，并且在1 mol/L的KOH溶液中能保持14 h的长时稳定性。这项工作可以促进过渡金属硫化物在电化学制氧过程中的应用。
- 电催化 /
- 析氧反应 /
- 硫化物 /
- 核壳结构 /
- 反应动力学
Abstract: Exploring non-precious metal oxygen evolution reaction (OER) electrocatalysts with high activity and stability is pivotal for electrolytic hydrogen production. Herein, we employ a photo-reduction deposition technique to load amorphous cobalt hydrogen phosphate (Co_xH_yPO₄, denoted as Co-Pi) onto the surface of porous NiCo₂S₄ (NCS) yolk-shell microspheres, successfully fabricating Co-Pi/NCS composite material. Through the integration of density functional theory (DFT) calculations with experimental investigations, the influence of Co-Pi introduction on the electronic structure and electrocatalytic performance of NCS is probed. The formation of heterogeneous interfaces and reconstruction of chemical bonds enhance the conductivity of Co-Pi/NCS, and modulate charge transfer between the catalyst and reaction intermediates, thereby altering adsorption strength and Gibbs free energy of the reaction, ultimately optimizing OER catalytic activity. Consequently, Co-Pi/NCS demonstrates commendable activity and durability, exhibiting low overpotential of 335 mV at current density of 10 mA·cm⁻² and maintaining prolonged stability for 14 hours in 1 mol/L KOH solution. This work holds promise for advancing the utilization of transition metal sulfides in electrochemical oxygen production processes.
- electrolysis /
- oxygen evolution reaction /
- sulfur compounds /
- core-shell structure /
- reaction kinetics

HTML全文

图 1 NiCo₂S₄ (NCS)和Co_xH_yPO₄/NiCo₂S₄ (Co-Pi/NCS)样品的XRD图谱 (a); NCS和1%Co-Pi/NCS的FTIR光谱 (b)

Figure 1. XRD patterns of NiCo₂S₄ (NCS) and Co_xH_yPO₄/NiCo₂S₄ (Co-Pi/NCS) samples (a). FTIR spectra of NCS and 1%Co-Pi/NCS (b)

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图 2 NiCo-MOF (a) 和NCS (b) 的SEM图像; NCS的N₂等温吸附曲线和孔径分布图 (c); 0.7%Co-Pi/NCS (d), 1%Co-Pi/NCS (e), 2%Co-Pi/NCS (f) 的SEM图像; NCS (g) 和1%Co-Pi/NCS (h) 的TEM图像; 1%Co-Pi/NCS的HRTEM图像 (i) 和EDS元素分布图 (图中标尺为200 nm) (j)

Figure 2. SEM images of NiCo-MOF (a) and NCS (b). N₂ isothermal adsorption curve and pore size distribution of NCS (c). SEM images of 0.7%Co-Pi/NCS (d), 1%Co-Pi/NCS (e), and 2%Co-Pi/NCS (f). TEM image of NCS (g) and 1%Co-Pi/NCS (h). HRTEM image (i) and EDS elemental mapping (the scale bars are 200 nm) (j) of 1%Co-Pi/NCS

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图 3 NCS和1%Co-Pi/NCS样品的Ni 2p (a), Co 2p (b), P 2p (c), S 2p (d) 高分辨XPS谱图

Figure 3. High resolution XPS spectra of Ni 2p (a), Co 2p (b), P 2p (c), S 2p (d) of NCS and 1%Co-Pi/NCS

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图 4 NCS和Co-Pi/NCS样品的LSV曲线 (a), Tafel斜率 (b), EIS曲线 (c) 和电化学双层电容 (C_dl) (d); NCS和1%Co-Pi/NCS样品在10 mA·cm⁻²电流密度下的计时电位曲线 (e) 以及800 min测试前后的LSV曲线 (f)

Figure 4. LSV curves (a), Tafel slopes (b), EIS plots (c), and C_dl (d) of NCS and Co-Pi/NCS samples. Chronopotential curve under current density of 10 mA·cm⁻² (e), and LSV curve before and after 800 min testing (f) of NCS and 1%Co-Pi/NCS

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图 5 NCS(100) (a), CoPO₄(010) (b) 和CoPO₄/NCS (c) 的晶体结构模型; CoPO₄/NCS的差分电荷密度 (d); NCS (e), CoPO₄ (f) 和CoPO₄/NCS (g) 的态密度; NCS (h), CoPO₄ (i) 和CoPO₄/NCS (j) 表面吸附中间体的稳定结构和自由能; NCS (k), CoPO₄ (l) 和CoPO₄/NCS (n) 表面吸附O原子的Bader电荷

Figure 5. Crystal structure of NCS(100) (a), CoPO₄(010) (b) and CoPO₄/NCS (c). Differential charge density of CoPO₄/NCS (d); Density of state of NCS (e), CoPO₄ (f) and CoPO₄/NCS (g); Stable structure and adsorption free energy of intermediates on NCS (h), CoPO₄ (i) and CoPO₄/NCS (j); Bader charges of NCS (k), CoPO₄ (l), and CoPO₄/NCS (n) adsorbed O atom

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表 1 Co_xH_yPO₄/NiCo₂S₄ (Co-Pi/NCS)与已报道的OER电催化剂在10 mA·cm⁻²电流密度下的过电位比较

Table 1. Comparison of the overpotentials to achieve the OER current density of 10 mA·cm⁻² for Co_xH_yPO₄/NiCo₂S₄ (Co-Pi/NCS) with reported electrocatalysts

Electrocatalyst	Electrolyte	P/mV	Reference
Co_xH_yPO₄/NiCo₂S₄	1 mol/L KOH	335	This work
NiCo₂S₄@double-layered carbon nanospheres	1 mol/L KOH	344	[16]
P-doped MnCo₂O₄	1 mol/L KOH	364	[28]
CoO/Co_xP	1 mol/L KOH	370	[29]
In-doped CoO/CoP	1 mol/L KOH	365	[30]
Co₆Ni₄P/nickel foam	1 mol/L KOH	373	[31]
Co₉S₈/MnS sulfur/nitrogen nitrogen co-doped carbon nanosheets	1 mol/L KOH	360	[32]
P-doped (Zn_0.33Ni_0.33Mn_0.33)Co₂O₄	1 mol/L KOH	349	[33]
NiO/NiCo₂O₄	1 mol/L KOH	350	[34]
NiCo₂S₄/reduced graphene oxide	1 mol/L KOH	366	[35]
P-doped manganese-cobalt oxide	1 mol/L KOH	520	[36]
NiCo₂O₄/N-doped carbon nanotubes/NiCo	1 mol/L KOH	350	[37]
Notes: P is the overpotential at the OER current density of 10 mA·cm⁻²

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