Metal鈥揙rganic Frameworks for Electrocatalytic Reduction of Carbon Dioxide

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• 作者：Nikolay Kornienko ; Yingbo Zhao ; Christopher S. Kley ; Chenhui Zhu ; Dohyung Kim ; Song Lin ; Christopher J. Chang ; Omar M. Yaghi ; Peidong Yang
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：November 11, 2015
• 年：2015
• 卷：137
• 期：44
• 页码：14129-14135
• 全文大小：508K
• ISSN：1520-5126

文摘

A key challenge in the field of electrochemical carbon dioxide reduction is the design of catalytic materials featuring high product selectivity, stability, and a composition of earth-abundant elements. In this work, we introduce thin films of nanosized metal鈥搊rganic frameworks (MOFs) as atomically defined and nanoscopic materials that function as catalysts for the efficient and selective reduction of carbon dioxide to carbon monoxide in aqueous electrolytes. Detailed examination of a cobalt鈥損orphyrin MOF, Al₂(OH)₂TCPP-Co (TCPP-H₂ = 4,4鈥?4鈥?4鈥?(porphyrin-5,10,15,20-tetrayl)tetrabenzoate) revealed a selectivity for CO production in excess of 76% and stability over 7 h with a per-site turnover number (TON) of 1400. In situ spectroelectrochemical measurements provided insights into the cobalt oxidation state during the course of reaction and showed that the majority of catalytic centers in this MOF are redox-accessible where Co(II) is reduced to Co(I) during catalysis.