Visible-Light Photoredox Catalysis: Selective Reduction of Carbon Dioxide to Carbon Monoxide by a Nickel N-Heterocyclic Carbene鈥揑soquinoline Complex

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• 作者：V. Sara Thoi ; Nikolay Kornienko ; Charles G. Margarit ; Peidong Yang ; Christopher J. Chang
• 刊名：Journal of the American Chemical Society
• 出版年：2013
• 出版时间：September 25, 2013
• 年：2013
• 卷：135
• 期：38
• 页码：14413-14424
• 全文大小：632K
• 年卷期：v.135,no.38(September 25, 2013)
• ISSN：1520-5126

文摘

The solar-driven reduction of carbon dioxide to value-added chemical fuels is a longstanding challenge in the fields of catalysis, energy science, and green chemistry. In order to develop effective CO₂ fixation, several key considerations must be balanced, including (1) catalyst selectivity for promoting CO₂ reduction over competing hydrogen generation from proton reduction, (2) visible-light harvesting that matches the solar spectrum, and (3) the use of cheap and earth-abundant catalytic components. In this report, we present the synthesis and characterization of a new family of earth-abundant nickel complexes supported by N-heterocyclic carbene鈥揳mine ligands that exhibit high selectivity and activity for the electrocatalytic and photocatalytic conversion of CO₂ to CO. Systematic changes in the carbene and amine donors of the ligand have been surveyed, and [Ni(^Prbimiq1)]²⁺ (1c, where ^Prbimiq1 = bis(3-(imidazolyl)isoquinolinyl)propane) emerges as a catalyst for electrochemical reduction of CO₂ with the lowest cathodic onset potential (E_cat = 鈭?.2 V vs SCE). Using this earth-abundant catalyst with Ir(ppy)₃ (where ppy = 2-phenylpyridine) and an electron donor, we have developed a visible-light photoredox system for the catalytic conversion of CO₂ to CO that proceeds with high selectivity and activity and achieves turnover numbers and turnover frequencies reaching 98,000 and 3.9 s^鈥?, respectively. Further studies reveal that the overall efficiency of this solar-to-fuel cycle may be limited by the formation of the active Ni catalyst and/or the chemical reduction of CO₂ to CO at the reduced nickel center and provide a starting point for improved photoredox systems for sustainable carbon-neutral energy conversion.