Isomorphous Cobalt Coordination Frameworks: Enhancing Electrocatalytic Oxygen Evolution Reaction through Coordinated Solvent Variations

IF 3.2 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
Anjana Chanthapally*, Anagha Yatheendran and N. Sandhyarani, 
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Abstract

Oxygen evolution reaction (OER) is a key electrochemical redox reaction involved in metal–air batteries and water-splitting devices. Reducing the energy barrier of these reactions accentuates the necessity in designing competent electrocatalysts. There is an urgent demand for affordable and durable catalysts utilizing non-noble metals, specifically Ni, Co, and Fe, for the OER. In this context, three following cobalt(II) coordination frameworks based on a pyridyl carboxylic acid ligand were synthesized: [Co33-OH)(PCA)4(DMF)2(H2O)](NO3)·DMF·3H2O (1), [Co33-OH)(PCA)4(EtOH)3](NO3)·3EtOH·3H2O (2), and [Co33-OH)(PCA)4(DMA)2(H2O)] (ClO4)·DMA·H2O) (3) using a solvothermal method. The single-crystal diffraction studies confirm the similarity in the three-center cobalt secondary building unit (SBU) and the final 3D topology. These frameworks are investigated as potential catalysts for the OER under alkaline (1 M KOH) conditions. Compound 1 shows extraordinary OER activity demonstrating an overpotential value of 0.37 V at 10 mA cm–2 and a Tafel slope of 78.9 mV. The alternation in the coordination sphere resulting from the difference in coordinated solvent emerges as an intriguing reason contributing to the exceptional activity of a coordination network. The effective electronic modulation within the cobalt trinuclear center induced by the changes in the coordination sphere has lowered the free energy barrier for the desorption of the oxygen produced. This work emphasizes the significant influence and effect of the coordination environment in catalytic activity, serving as a template for designing advanced electrocatalysts that are free from noble metals.

Abstract Image

同形钴配位框架:通过配位溶剂变化增强电催化析氧反应
析氧反应(OER)是金属-空气电池和水分解装置中重要的电化学氧化还原反应。降低这些反应的能垒突出了设计胜任电催化剂的必要性。对于使用非贵金属,特别是Ni, Co和Fe,用于OER的可负担且耐用的催化剂有迫切的需求。在此背景下,采用溶剂热法合成了三个基于吡啶羧酸配体的钴(II)配位框架:[Co3(μ3-OH)(PCA)4(DMF)2(H2O)](NO3)·DMF·3H2O (1), [Co3(μ3-OH)(PCA)4(EtOH)3](NO3)·3EtOH·3H2O(2)和[Co3(μ3-OH)(PCA)4(DMA)2(H2O)] (ClO4)·DMA·H2O)(3)。单晶衍射研究证实了三中心钴二级构建单元(SBU)和最终三维拓扑结构的相似性。在碱性(1 M KOH)条件下,研究了这些框架作为OER的潜在催化剂。化合物1在10 mA cm-2下的过电位值为0.37 V, Tafel斜率为78.9 mV。配位溶剂的不同所导致的配位域的变化是导致配位网络异常活性的一个有趣的原因。配位球的变化引起钴三核中心内的有效电子调制降低了氧解吸的自由能垒。这项工作强调了配位环境对催化活性的重要影响和作用,为设计不含贵金属的先进电催化剂提供了模板。
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来源期刊
Crystal Growth & Design
Crystal Growth & Design 化学-材料科学:综合
CiteScore
6.30
自引率
10.50%
发文量
650
审稿时长
1.9 months
期刊介绍: The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials. Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.
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