基于Cu(II)Tricine配合物制备氧化铜薄膜及其电催化水氧化活性

引用本文: 高岩, 陈虎, 叶璐, 路忠凯, 姚亚男, 魏宇, 陈旭阳. 基于Cu(II)Tricine配合物制备氧化铜薄膜及其电催化水氧化活性[J]. 催化学报, 2018, 39(3): 479-486. doi: 10.1016/S1872-2067(17)62892-4 shu

Citation: Yan Gao, Hu Chen, Lu Ye, Zhongkai Lu, Yanan Yao, Yu Wei, Xuyang Chen. Highly effective electrochemical water oxidation by copper oxide film generated in situ from Cu(II) tricine complex[J]. Chinese Journal of Catalysis, 2018, 39(3): 479-486. doi: 10.1016/S1872-2067(17)62892-4 shu

基于Cu(II)Tricine配合物制备氧化铜薄膜及其电催化水氧化活性

大连理工大学精细化工国家重点实验室, 人工光作用研究所, 大连理工大学-瑞典皇家工学院分子器件联合中心, 辽宁大连 116024
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（21573033）；辽宁省重点实验室基础研究项目（LZ2015015）.

摘要: 众所周知，传统化石燃料的大量使用不仅导致严重的环境污染和温室效应，而且化石能源本身也面临着枯竭的危机.所以，探索全新的、环境友善的、可持续发展的能源载体一直备受国内外科研工作者的关注.氢能是一种清洁的可再生能源，是有潜力的化石能源替代品.水分解是一种有效的、理想的产氢途径，然而水氧化反应是多质子多电子传递的过程，是制约整个水分解过程的瓶颈.目前，基于贵金属（铱和钌）分子和氧化物的电催化剂已经被报道很多，并且可以保持很好的催化活性；但是，这一类催化剂差的稳定性、昂贵的价格和少的地壳含量等因素严重制约了其大规模实际应用.因此，开发基于非贵金属（钴、镍、铁、铜、锰）的新型电催化剂材料是解决该问题的唯一出路，但要保证电催化剂的高活性和好的稳定性仍面临着诸多挑战.
在众多的非贵金属中，铜是一种来源广泛的金属，而且铜对生物体毒性较小.由于铜具有良好的配位化学和多重的氧化还原特性，近年来，很多基于铜的水氧化电催化剂被开发和研究.
我们在含有1.0mmol/L Cu²⁺和2.0mmol/L Tris配体的磷酸缓冲溶液（0.2mol/L，pH=12.0）中，采用1.15 V vs.NHE恒电位电沉积的方法，在ITO导电玻璃上制备出基于铜的水氧化催化剂薄膜（Cu-tricine）.对得到的催化剂薄膜进行扫描电镜（SEM）测试，该催化剂均匀负载在ITO表面，厚度大约是1.4μm.为了更加深入研究Cu-Tricine催化剂薄膜，采用透射电子显微镜（TEM）和X射线衍射（XRD）对Cu-tricine催化剂进行表征，结果表明，该催化剂薄膜是一种结晶度较差的无定形材料.同时，为了研究催化剂薄膜的元素组成及其所处状态，对催化剂进行了能量散射X射线能谱（EDX）和X射线光电子能谱（XPS）测试，结果表明，该催化剂由铜和氧元素组成，并且铜是以正二价存在.由高分辨O1sXPS谱图分析结果可以推测，Cu-Tricine催化剂可能是由氧化铜和氢氧化铜组成.Cu-tricine催化剂的水氧化活性是在0.2mol/L的磷酸缓冲溶液（pH=12.0）中进行测试，从塔菲尔曲线中可以得出，该催化剂达到1.0mA/cm²的催化电流密度所需的过电位是395mV，塔菲尔斜率为46.7mV/decade.此外，在1.15 V vs.NHE的电位下，在10h的电解过程中，Cu-tricine催化剂薄膜可以将催化电流密度一直保持在7.5mA/cm²，并且得到的法拉第效率为99%.

关键词:

English

Highly effective electrochemical water oxidation by copper oxide film generated in situ from Cu(II) tricine complex

State Key Laboratory of Fine Chemicals, Institute of Artificial Photosynthesis, DUT-KTH Joint Education and Research Center on Molecular Devices, Dalian University of Technology(DUT), Dalian 116024, Liaoning, China
Received Date: 28 October 2017
Revised Date: 20 November 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 (21573033), and the Basic Research Project of Key Laboratory of Liaoning (LZ2015015).

Abstract: Developing highly efficient and stable water oxidation catalysts based on abundant metallic elements is a challenge that must be met to fulfill the promise of water splitting for clean energy production. In this work, we developed an oxygen evolution reaction catalyst consisting of a nanostructured film electrodeposited from a phosphate buffer solution (0.2 mol/L, pH=12.0) containing Cu-tricine complex. A Tafel plot showed that the required overpotential for a current density of 1.0 mA/cm² was only 395 mV and the Tafel slope was 46.7 mV/decade. In addition, the Cu-tricine film maintained a stable current density of 7.5 mA/cm² for the oxygen evolution reaction in phosphate buffer solution for 10 h, and a Faradaic efficiency of 99% was obtained.

Key words:

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基于Cu(II)Tricine配合物制备氧化铜薄膜及其电催化水氧化活性

English

Highly effective electrochemical water oxidation by copper oxide film generated in situ from Cu(II) tricine complex

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基于Cu(II)Tricine配合物制备氧化铜薄膜及其电催化水氧化活性

English

Highly effective electrochemical water oxidation by copper oxide film generated in situ from Cu(II) tricine complex

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

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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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