Molecular Cluster Complex of High-Valence Chromium Selenide Carbonyl as Effective Electrocatalyst for Water Oxidation
Molecular Cluster Complex of High-Valence Chromium Selenide Carbonyl as Effective Electrocatalyst for Water Oxidation
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DOI：
10.3390/catal13040721
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发表时间：
2023-04
期刊：
影响因子：
3.9
通讯作者：
Ibrahim M. Abdullahi;M. Nath
中科院分区：
文献类型：
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作者：
Ibrahim M. Abdullahi;M. Nath
开发简单、经济、环保、具有高内在活性和低过电位的水氧化电催化剂一直是研究的热点。在本文中，二硒化三铬羰基团簇配合物（Et4N）2[Se2Cr3(CO)10]具有独特的键结结构，由桥接Se基团组成，被认为是一种很有前途的析氧反应（OER）电催化剂。该羰基团簇在10 mAcm−2下具有310 mV的过电位和82.0 mV dec−1的低塔菲尔斜率，在碱性介质中具有优异的耐久性，可以长时间连续析氧。在0.390 V vs. RHE下，质量活度和周转率分别达到62.2 Ag−1和0.0174 s−1。本文报道的Cr-配合物显示出明显不同的催化活性，这是基于催化活性Cr位点周围配体化学的细微变化。这种依赖性进一步证实了配体配位对电子密度分布的重要影响，进而影响活性位点的电化学活化和催化效率。具体来说，即使是电负性更强的取代基的部分取代也会导致催化效率的减弱。本报告进一步证明，金属羰基硫族化合物簇型材料具有部分占据的位点和金属位点的高价位，可以作为催化活性中心，催化OER具有较高的本征活性。从本报告中产生的见解可以直接外推到含有类似结构基元的三维固体，从而有助于优化催化剂设计。
Developing simple, affordable, and environmentally friendly water oxidation electrocatalysts with high intrinsic activity and low overpotential continues to be an area of intense research. In this article, a trichromium diselenide carbonyl cluster complex (Et4N)2[Se2Cr3(CO)10], with a unique bonding structure comprising bridging Se groups, has been identified as a promising electrocatalyst for oxygen evolution reaction (OER). This carbonyl cluster exhibits a promising overpotential of 310 mV and a low Tafel slope of 82.0 mV dec−1 at 10 mAcm−2, with superior durability in an alkaline medium, for a prolonged period of continuous oxygen evolution. The mass activity and turnover frequency of 62.2 Ag−1 and 0.0174 s−1 was achieved, respectively at 0.390 V vs. RHE. The Cr-complex reported here shows distinctly different catalytic activity based on subtle changes in the ligand chemistry around the catalytically active Cr site. Such dependence further corroborates the critical influence of ligand coordination on the electron density distribution which further affects the electrochemical activation and catalytic efficiency of the active site. Specifically, even partial substitution with more electronegative substituents leads to the weakening of the catalytic efficiency. This report further demonstrates that metal carbonyl chalcogenides cluster-type materials which exhibit partially occupied sites and high valence in their metal sites can serve as catalytically active centers to catalyze OER exhibiting high intrinsic activity. The insight generated from this report can be directly extrapolated to 3-dimensional solids containing similar structural motifs, thereby aiding in optimal catalyst design.