Organometallic Ni Pincer Complexes for the Electrocatalytic Production of Hydrogen

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• 作者：Oana R. Luca ; James D. Blakemore ; Steven J. Konezny ; Jeremy M. Praetorius ; Timothy J. Schmeier ; Glendon B. Hunsinger ; Victor S. Batista ; Gary W. Brudvig ; Nilay Hazari ; Robert H. Crabtree
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：August 20, 2012
• 年：2012
• 卷：51
• 期：16
• 页码：8704-8709
• 全文大小：296K
• 年卷期：v.51,no.16(August 20, 2012)
• ISSN：1520-510X

文摘

Nonplatinum metals are needed to perform cost-effective water reduction electrocatalysis to enable technological implementation of a proposed hydrogen economy. We describe electrocatalytic proton reduction and H₂ production by two organometallic nickel complexes with tridentate pincer ligands. The kinetics of H₂ production from voltammetry is consistent with an overall third order rate law: the reaction is second order in acid and first order in catalyst. Hydrogen production with 90鈥?5% Faradaic yields was confirmed by gas analysis, and UV鈥搗is spectroscopy suggests that the ligand remains bound to the catalyst over the course of the reaction. A computational study provides mechanistic insights into the proposed catalytic cycle. Furthermore, two proposed intermediates in the proton reduction cycle were isolated in a representative system and show a catalytic response akin to the parent compound.