分子前驱体衍生的氧化镍电极催化水氧化性能研究

引用本文: 李斐, 李华, 朱勇, 杜健, 王勇, 孙立成. 分子前驱体衍生的氧化镍电极催化水氧化性能研究[J]. 催化学报, 2017, 38(11): 1812-1817. doi: 10.1016/S1872-2067(17)62921-8 shu

Citation: Fei Li, Hua Li, Yong Zhu, Jian Du, Yong Wang, Licheng Sun. Electrocatalytic water oxidation by a nickel oxide film derived from a molecular precursor[J]. Chinese Journal of Catalysis, 2017, 38(11): 1812-1817. doi: 10.1016/S1872-2067(17)62921-8 shu

分子前驱体衍生的氧化镍电极催化水氧化性能研究

李斐 ^a, ,
李华 ^a, ,
朱勇 ^a, ,
杜健 ^a, ,
王勇 ^a, ,
孙立成 ^a,b,

a 大连理工大学精细化工国家重点实验室, 辽宁大连 116024;
b 瑞典皇家工学院化学系, 斯德哥尔摩 10044, 瑞典
基金项目:
国家重点基础研究发展计划（973计划，2014CB239402）；国家自然科学基金（21476043）.

摘要: 太阳能分解水制氢是解决当前能源和环境危机的潜在手段之一.其中由于水氧化半反应涉及4个电子和4个质子的转移，因此是全分解水反应的瓶颈所在.为了发展高效的水氧化催化剂，降低水氧化过电位，人们付出了巨大的努力.目前活性最高的水氧化催化剂都是基于钌和铱的贵金属催化剂，高昂的成本阻碍了这些催化剂的规模化应用，因此人们尝试利用各种方法制备基于廉价金属的水氧化催化剂.2008年，Nocera课题组利用电沉积法从磷酸溶液中得到了高活性氧化钴催化剂，之后该法逐渐得到推广.最近，Spiccia和Allen课题组利用分子前驱体通过电沉积法制备了氧化镍催化剂，但其催化活性和稳定性有待进一步提高.本文将一个简单的镍配合物[Ni （en）₃]Cl₂（en=1，2-乙二胺）作为前驱体溶解到磷酸缓冲溶液中，在FTO基底上电沉积得到具有高催化活性的氧化镍水氧化催化剂.
在pH=11的磷酸缓冲溶液中，由分子前驱体沉积所得到的NiO_x的催化电流达到1 mA/cm²时的过电位为375 mV，且可稳定工作10 h以上.其催化过程中的Tafel斜率为46 mV/decade，表现出优异的动力学特性.该电极和之前文献中催化活性最高的从分子前驱体衍生得到的NiO_x相比展现出较大的优势.比如在1.3 V （相对于NHE）电压下，[Ni （en）₃]Cl₂衍生的NiO_x催化电流密度可以达到8.5 mA/cm²，法拉第效率为98%.而Ni-氨基乙酸衍生的NiO_x在相同条件下催化电流密度为4 mA/cm²，法拉第效率仅为60%.该工作充分证明以分子配合物作为前驱体是制备高效高稳定性多相水氧化催化剂的简便途径.有机配体和金属螯合的分子前驱体在结构上具有灵活可调的特性，从而有助于构建活性和效率更高的催化体系.

关键词:

English

Electrocatalytic water oxidation by a nickel oxide film derived from a molecular precursor

Fei Li ^a, ,
Hua Li ^a, ,
Yong Zhu ^a, ,
Jian Du ^a, ,
Yong Wang ^a, ,
Licheng Sun ^a,b,

a State Key Laboratory of Fine Chemicals, DUT-KTH Joint Education and Research Center on Molecular Devices, Dalian University of Technology(DUT), Dalian 116024, Liaoning, China;
b Department of Chemistry, School of Chemical Science and Engineering, KTH Royal Institute of Technology, Stockholm 10044, Sweden
Received Date: 30 August 2017
Revised Date: 25 September 2017
Fund Project:
This work was supported by the National Basic Research Program of China (973 program, 2014CB239402), the National Natural Science Foundation of China (21476043), and the Swedish Energy Agency and K&A Wallenberg Foundation

Abstract: In this study, we fabricated a NiO_x film by electrodeposition of an ethanediamine nickel complex precursor (pH=11) on a fluorine-doped tin oxide substrate. The resulting film is robust and exhib-its high catalytic activity for electrochemical water oxidation. Water oxidation is initiated with an overpotential of 375 mV (1 mA/cm²) and a steady current density of 8.5 mA/cm² is maintained for at least 10 h at 1.3 V versus the normal hydrogen electrode. Kinetic analysis reveals that there is a 2e^-/3H⁺ pre-equilibrium process before the chemical rate-determining step. The low-cost preparation, robustness, and longevity make this catalyst competitive for applications in solar energy conversion and storage.

Key words:

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分子前驱体衍生的氧化镍电极催化水氧化性能研究

English

Electrocatalytic water oxidation by a nickel oxide film derived from a molecular precursor

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CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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中国化学会秘书处

分子前驱体衍生的氧化镍电极催化水氧化性能研究

English

Electrocatalytic water oxidation by a nickel oxide film derived from a molecular precursor

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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