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金属有机框架衍生的双金属氧化物CuCoO作为析氧反应的高效电催化剂。

Metal-organic framework derived bimetal oxide CuCoO as efficient electrocatalyst for the oxygen evolution reaction.

作者信息

Gao Han, Yang Miao, Du Zijuan, Liu Xing, Dai Xianglong, Lin Kun, Bao Xiao-Qing, Li Hong, Xiong Dehua

机构信息

State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, P. R. China.

Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan 430074, P. R. China.

出版信息

Dalton Trans. 2022 Apr 12;51(15):5997-6006. doi: 10.1039/d2dt00517d.

Abstract

Metal-organic framework (MOF) materials with tunable porous morphology, controlled crystalline structure, various compositions, and high specific surface area are widely used as precursors to synthesize electrocatalysts for water splitting, which is beneficial for improving their oxygen evolution reaction (OER) performance. Using ZIF-67 as a Co source and Cu-BTC as a Cu source, hexagonal MOF-derived CuCoO (MOF-CCO) nanocrystals with the size of ∼288 nm were prepared through a one-step solvothermal method. The influence of the content of the precursor solvents (absolute ethanol and deionized water), reaction temperature, mass ratio of reactants, NaOH addition, and reactant concentration of precursors on the structure and morphology of the products was investigated. The optimal CuCoO nanocrystals (MOF-CCO1) around 288 nm present the highest OER activity, such as a low overpotential of 364.7 mV at 10 mA cm, a small Tafel slope of 64.1 mV dec, and attractive durability in 1.0 M KOH solution. The XPS results showed that the higher catalytic efficiency of MOF-CCO1 nanocrystals could be due to the oxygen vacancies caused by lattice oxygen loss, the increase of OH content on the surface, and the synergistic effect of Cu/Cu and Co/Co redox pairs. Finally, a possible OER mechanism for MOF-CCO nanocrystals of water splitting was proposed. This study provides a new approach for the preparation of delafossite nanomaterials and for the improvement of their OER performances.

摘要

具有可调节多孔形态、可控晶体结构、多种组成和高比表面积的金属有机框架(MOF)材料被广泛用作合成用于水分解的电催化剂的前驱体,这有利于提高其析氧反应(OER)性能。以ZIF-67作为钴源、Cu-BTC作为铜源,通过一步溶剂热法制备了尺寸约为288 nm的六方MOF衍生的CuCoO(MOF-CCO)纳米晶体。研究了前驱体溶剂(无水乙醇和去离子水)的含量、反应温度、反应物质量比、NaOH添加量以及前驱体反应物浓度对产物结构和形貌的影响。约288 nm的最佳CuCoO纳米晶体(MOF-CCO1)表现出最高的OER活性,例如在10 mA cm时过电位低至364.7 mV,塔菲尔斜率小至64.1 mV dec,并且在1.0 M KOH溶液中具有良好的耐久性。XPS结果表明,MOF-CCO1纳米晶体较高的催化效率可能归因于晶格氧损失导致的氧空位、表面OH含量的增加以及Cu/Cu和Co/Co氧化还原对的协同作用。最后,提出了MOF-CCO纳米晶体水分解可能的OER机理。该研究为制备铜铁矿纳米材料及其OER性能的改善提供了一种新方法。

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