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

doi:10.13801/j.cnki.fhclxb.20240717.002

无定形Co_xH_yPO₄复合NiCo₂S₄核壳结构设计及其电催化析氧性能

doi: 10.13801/j.cnki.fhclxb.20240717.002

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: 54
- HTML全文浏览量: 43
- PDF下载量: 5
- 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: 2024-07-18
- 刊出日期: 2024-11-15

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, China

Funds: National Natural Science Foundation of China (22309204; 22209203); China Postdoctoral Science Foundation (2023M733742); Material Science and Engineering Discipline Guidance Fund of China University of Mining and Technology (CUMTMS202202; 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 (a) NiCo₂S₄ (NCS)和Co_xH_yPO₄/NiCo₂S₄ (Co-Pi/NCS)样品的XRD图谱；(b) NCS和1%Co-Pi/NCS的FTIR图谱

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

下载: 全尺寸图片幻灯片

图 2 NiCo-MOF (a) 和NCS (b) 的SEM图像；NCS的N₂等温吸脱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(j)

Figure 2. SEM images of NiCo-MOF (a) and NCS (b); N₂ isothermal adsorption curves 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 images of NCS (g) and 1%Co-Pi/NCS (h); HRTEM image (i) and EDS elemental mapping (j) of 1%Co-Pi/NCS

下载: 全尺寸图片幻灯片

图 3 NCS和1%Co-Pi/NCS样品的Ni2p (a)、Co2p (b)、P2p (c)、S2p (d) 高分辨XPS图谱

Figure 3. High resolution XPS spectra of Ni2p (a), Co2p (b), P2p (c), S2p (d) of NCS and 1%Co-Pi/NCS

下载: 全尺寸图片幻灯片

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) 及800 min测试前后的LSV曲线 (f)

J—Current density; Z'—Real part of impedance; Z''—Imaginary part of impedance; RHE—Reversible hydrogen electrode

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

下载: 全尺寸图片幻灯片

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

E_fermi—Fermi energy; TDOS—Total density of state

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

下载: 全尺寸图片幻灯片

表 1 Co_xH_yPO₄复合NiCo₂S₄核壳结构(Co-Pi/NCS)样品制备参数

Table 1. Preparation parameter for Co_xH_yPO₄ complex NiCo₂S₄ core-shell structure (Co-Pi/NCS) sample

Sample	m_NCS/mg	V_PBS/mL	V_Co/μL	Co-Pi content/wt%
0.7%Co-Pi/NCS	10	15	26.25	0.7
1%Co-Pi/NCS	10	15	37.5	1
2%Co-Pi/NCS	10	15	75	2
Notes: m_NCS—Mass of NCS; V_PBS—Volume of phosphate buffer solution (0.1 mol/L); V_Co—Volume of Co(NO₃)₂·6H₂O solution (0.5 mmol/L).

下载: 导出CSV

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

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

Electrocatalyst	Electrolyte	P/mV	Ref.
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]
Note: P—Overpotential at the OER current density of 10 mA·cm⁻².

下载: 导出CSV

参考文献(37)

[1]	ZANG Y, LU D Q, WANG K, et al. A pyrolysis-free Ni/Fe bimetallic electrocatalyst for overall water splitting[J]. Nature Communications, 2023, 14: 1792. doi: 10.1038/s41467-023-37530-9
[2]	赖嘉俊, 李潇潇, 曾传旺, 等. 富氧空位铁基复合材料的制备及其电催化析氢性能[J]. 复合材料学报, 2023, 40(5): 2827-2835. LAI Jiajun, LI Xiaoxiao, ZENG Chuanwang, et al. Preparation of oxygen-rich vacancy iron-matrix composites and their electrocatalytic hydrogen evolution properties[J]. Acta Materiae Compositae Sinica, 2023, 40(5): 2827-2835 (in Chinese).
[3]	PONNADA S, KIAI M S, GORLD D B, et al. Recent status and challenges in multifunctional electrocatalysis based on 2D MXenes[J]. Catalysis Science & Technology, 2022, 12(14): 4413-4441.
[4]	DENG Y W, CAO Y F, XIA Y, et al. Self-templated synthesis of CoFeP@C cage-in-cage superlattices for enhanced electrocatalytic water splitting[J]. Advanced Energy Materials, 2022, 12: 2202394. doi: 10.1002/aenm.202202394
[5]	张海成, 杨邦志, 张娇, 等. 钴掺杂铜基复合材料的制备及其电催化析氧性能[J]. 复合材料学报, 2024, 41(4): 1923-1933. ZHANG Haicheng, YANG Bangzhi, ZHANG Jiao, et al. Synthesis and electrocatalytic oxygen evolution performance of cobalt doped copper-based composites[J]. Acta Materiae Compositae Sinica, 2024, 41(4): 1923-1933(in Chinese).
[6]	姜金池, 金彪, 孟龙月. 基于电催化析氧反应的非贵金属催化剂研究进展[J]. 复合材料学报, 2023, 40(3): 1365-1380. JIANG Jinchi, JIN Biao, MENG Longyue. Research progress on non-noble metal catalysts based on electrocatalytic oxygen evolution reactions[J]. Acta Materiae Compositae Sinica, 2023, 40(3): 1365-1380 (in Chinese).
[7]	CAI X Y, ZENG Z T, LIU Y D, et al. Visible-light-driven water splitting by yolk-shelled ZnIn₂S₄-based heterostructure without noble-metal co-catalyst and sacrificial agent[J]. Applied Catalysis B: Environmental, 2021, 297: 120391.
[8]	DAI W J, PAN Y, REN K, et al. Heteroatom Ni alloyed pyrite-phase FeS₂ as a precatalyst for enhanced oxygen evolution reaction[J]. Electrochimica Acta, 2020, 355: 136821. doi: 10.1016/j.electacta.2020.136821
[9]	LAN M Q, XIE C Y, LI B, et al. Two-dimensional cobalt sulfide/iron-nitrogen-carbon holey sheets with improved durability for oxygen electrocatalysis[J]. ACS Applied Materials & Interfaces, 2022, 14(9): 11538-11546.
[10]	LIN J H, WANG H H, CAO J, et al. Engineering Se vacancies to promote the intrinsic activities of P doped NiSe₂ nanosheets for overall water splitting[J]. Journal of Colloid and Interface Science, 2020, 571: 260-266. doi: 10.1016/j.jcis.2020.03.053
[11]	EL-REFAEI S M, RUSSO P A, PINNA N. Recent advances in multimetal and doped transition-metal phosphides for the hydrogen evolution reaction at different pH values[J]. ACS Applied Materials & Interfaces, 2021, 13(19): 22077-22097.
[12]	MA G Y, YE J T, QIN M Y, et al. Mn-doped NiCoP nanopin arrays as high-performance bifunctional electrocatalysts for sustainable hydrogen production via overall water splitting[J]. Nano Energy, 2023, 115: 108679. doi: 10.1016/j.nanoen.2023.108679
[13]	LIN Y, CHEN X M, TUO Y X, et al. In-situ doping-induced lattice strain of NiCoP/S nanocrystals for robust wide pH hydrogen evolution electrocatalysis and supercapacitor[J]. Journal of Energy Chemistry, 2022, 70: 27-35. doi: 10.1016/j.jechem.2022.02.024
[14]	CHEN T, WEI S T, WANG Z H. NiCo₂S₄-based composite materials for supercapacitors[J]. ChemPlusChem, 2020, 85(1): 43-56. doi: 10.1002/cplu.201900288
[15]	孙兴伟, 白杰, 李春萍, 等. 钴基电极材料的改性策略及其应用研究[J]. 复合材料学报, 2023, 40(5): 2550-2565. SUN Xingwei, BAI Jie, LI Chunping, et al. Modification strategy and application of cobalt-based electrode materials[J]. Acta Materiae Compositae Sinica, 2023, 40(5): 2550-2565 (in Chinese).
[16]	CHEN Y T, WU H Y, TANG N, et al. A NiCo₂S₄ octahedral configuration doped by Mn, Zn and Cu for the oxygen evolution reaction[J]. Chemical Communiations, 2024, 60: 1751.
[17]	LIU C C, ZHANG X, HAO X Q, et al. NiCO₂S₄ nanotubes in situ anchored double-layered hollow carbon nanospheres towards enhanced overall water splitting[J]. Journal of Alloys and Compounds, 2024, 1002: 175110. doi: 10.1016/j.jallcom.2024.175110
[18]	BAI L, SONG A L, LEI X Y, et al. Hierarchical construction of hollow NiCo₂S₄ nanotube@NiCo₂S₄ nanosheet arrays on Ni foam as an efficient and durable electrocatalyst for hydrogen evolution reaction[J]. International Journal of Hydrogen Energy, 2022, 47(19): 38524-38532.
[19]	SONG W J, XU M Z, TENG X, et al. Construction of self-supporting, hierarchically structured caterpillar-like NiCo₂S₄ arrays as an efficient trifunctional electrocatalyst for water and urea electrolysis[J]. Nanoscale, 2021, 13(3): 1680-1688.
[20]	李群, 张阔, 李艳华, 等. 三维多级钴酸镍结构的形貌调控及其电化学性能[J]. 复合材料学报, 2024, 41(1): 281-292. LI Qun, ZHANG Kuo, LI Yanhua, et al. Morphology control and electrochemical properties of three-dimensional hierarchical NiCo₂O₄ structure[J]. Acta Materiae Compositae Sinica, 2024, 41(1): 281-292 (in Chinese).
[21]	JIANG R Q, MAO L, ZHAO Y L, et al. Spatial carrier separation in cobalt phosphate deposited ZnIn₂S₄ nanosheets for efficient photocatalytic hydrogen evolution[J]. Journal of Colloid and Interface Science, 2022, 606: 317-327. doi: 10.1016/j.jcis.2021.08.008
[22]	RADHIKA M G, SRILAKSHMI R, TEJASHREE V, et al. A new strategy for the morphology-controlled synthesis of Ni/Co MOFs for high-performance asymmetric supercapacitors[J]. Journal of Energy Storage, 2023, 61: 106766. doi: 10.1016/j.est.2023.106766
[23]	BLOCHL P E. Projector augmented-wave method[J]. Physical Review B, 1994, 50: 17953-17979.
[24]	龙升, 刘依, 邹攀, 等. 球状NiCo₂S₄的制备及其在KOH溶液中的电化学行为[J/OL]. 复合材料学报, 1-8[2024-09-29]. https://doi.org/10.13801/j.cnki.fhclxb.20240626.002. LONG Sheng, LIU Yi, ZOU Pan, et al. Preparation of spherical NiCo₂S₄ and the electrochemical behavior in KOH solution[J/OL]. Acta Materiae Compositae Sinica, 1-8[2024-09-29]. https://doi.org/10.13801/j.cnki.fhclxb.20240626.002 (in Chinese).
[25]	朱彬, 刘盼, 吕东风. NiCo₂O₄纳米线/SiC复合纤维制备及其电化学性能[J]. 复合材料学报, 2020, 37(7): 1684-1694. ZHU Bin, LIU Pan, LYU Dongfeng. Preparation and electrochemistry properties of NiCo₂O₄ nanowire/SiC composite fiber[J]. Acta Materiae Compositae Sinica, 2020, 37(7): 1684-1694 (in Chinese).
[26]	CHEN J, MAO L, XU J C, et al. Synergetic effect of phosphorus-dopant and graphene-covering layer on hydrogen evolution activity and durability of NiCo₂S₄ electrocatalysts[J]. Science China Materials, 2023, 66(10): 3875-3886. doi: 10.1007/s40843-023-2546-3
[27]	LU X F, ZHANG S L, SIM W L, et al. Phosphorized CoNi₂S₄ yolk-shell spheres for highly efficient hydrogen production via water and urea electrolysis[J]. Angewandte Chemie International Edition, 2021, 60(42): 22885-22891. doi: 10.1002/anie.202108563
[28]	YAO L L, YANG W X, NIU Y J, et al. Comparison of the effects of cation and phosphorus doping in cobalt-based spinel oxides towards the oxygen evolution reaction[J]. CrystEngComm, 2021, 23: 1849-1858. doi: 10.1039/D0CE01771J
[29]	NIU Y, XIAO M L, ZHU J B, et al. A "trimurti" heterostructured hybrid with an intimate CoO/Co_xP interface as a robust bifunctional air electrode for rechargeable Zn-air batteries[J]. Journal of Materials Chemistry A, 2020, 8: 9177-9184. doi: 10.1039/D0TA01145B
[30]	JIN W, CHEN J P, LIU B, et al. Oxygen vacancy-rich in-doped CoO/CoP heterostructure as an effective air cathode for rechargeable Zn-air batteries[J]. Small, 2019, 15: 1904210. doi: 10.1002/smll.201904210
[31]	JIA F H, ZOU X Y, WEI X Y, et al. Synergistic effect of P doping and Mo-Ni-based heterostructure electrocatalyst for overall water splitting[J]. Materials, 2023, 16(9): 3411. doi: 10.3390/ma16093411
[32]	LI J C, LI W Q, MI H W, et al. Bifunctional oxygen electrocatalysis on ultra-thin Co₉S₈/MnS carbon nanosheets for all-solid-state zinc-air batteries[J]. Journal of Materials Chemistry A, 2021, 9: 22635-22642. doi: 10.1039/D1TA07019C
[33]	GUO Z, PANG Y Y, XIE H, et al. Phosphorus-doped CuCo₂O₄ oxide with partial amorphous phase as a robust electrocatalyst for the oxygen evolution reaction[J]. ChemElectroChem, 2021, 8: 135-141. doi: 10.1002/celc.202001312
[34]	ZHANG L G, PANG D, CAO X L, et al. Phosphorus modified hollow, porous nickel-cobalt oxides nanocubes with heterostructure for oxygen evolution reaction in alkaline[J]. Journal of Alloys and Compounds, 2022, 925: 166338. doi: 10.1016/j.jallcom.2022.166338
[35]	ZHAO S, MO Z L, NIU X H, et al. Hierarchical NiCo₂S₄ nanosheets grown on graphene to catalyze the oxygen evolution reaction[J]. Energy Materials, 2020, 55: 1627-1636.
[36]	PENG X F, WANG Z. Facile route of P-doped defect-rich manganese-cobalt oxide spinel with enhanced oxygen evolution reaction performance[J]. ChemNanoMat, 2020, 6(12): 1812-1818. doi: 10.1002/cnma.202000475
[37]	CHEN C, SU H, LU L N, et al. Interfacing spinel NiCo₂O₄ and NiCo alloy derived N-doped carbon nanotubes for enhanced oxygen electrocatalysis[J]. Chemical Engineering Journal, 2021, 408: 127814-127823. doi: 10.1016/j.cej.2020.127814