Repurposing a Bio-Inspired NiFe Hydrogenase Model for CO2 Reduction with Selective Production of Methane as the Unique C-Based Product
Repurposing a Bio-Inspired NiFe Hydrogenase Model for CO2 Reduction with Selective Production of Methane as the Unique C-Based Product
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DOI：
10.1021/acsenergylett.0c02002
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发表时间：
2020-12-11
影响因子：
22
通讯作者：
Duboc, Carole
中科院分区：
文献类型：
--
作者：
Ahmed, Md Estak;Adam, Suzanne;Duboc, Carole
在当前的环境和经济背景下，迫切需要开发催化体系，以有效地活化和转化大量的小分子，同时在涉及多电子过程时表现出选择性。这对于由CO2催化生产CH 4尤其如此，因为迄今为止已经描述了有限数量的活性光催化剂或电催化剂。在此，我们报告了物理吸附在石墨电极上的分子电催化剂的前所未有的反应性：生物启发的[（LNiFeCp）-Ni-N2 S2-Fe-II-Cp-II（CO）]+（L-N2 S2 = 2，2 '-（2，2'-联吡啶-6，6 '-二基）双-（1，1'-二苯基乙硫醇盐）络合物选择性地催化还原酸性水溶液中的CO2以产生CH 4和H-2的混合物。在优化的条件下，在pH 4时，测量到CH 4和H-2的法拉第产率分别为12%和66%（TOFCH 4 = 214 s（-1），TOFH 2约为5.1 × 10（3）s（-1））。我们证明，这种双核NiFe催化剂在受控电位电解条件下稳定数小时。
In the current environmental and economic context, there is an urgent need to develop catalytic systems to efficiently activate and transform abundant small molecules while demonstrating selectivity when multielectron processes are involved. This is especially true for catalytic production of CH4 from CO2, as a limited number of active photo- or electro-catalysts have been described to date. Herein, we report the unprecedented reactivity of a molecular electrocatalyst physiadsorbed on a graphite electrode: the bioinspired [(LNiFeCp)-Ni-N2S2-Fe-II-Cp-II(CO)]+ (L-N2S2 = 2,2'-(2,2'-bipryridine-6,6'-diyl)bis- (1,1'-diphenylethanethiolate) complex selectively and catalytically reduces CO2 in acidic aqueous solution to produce a mixture of CH4 and H-2. Under optimized conditions, at pH 4, Faradaic yields of 12% and 66% for CH4 and H-2 production (TOFCH4 = 214 s(-1), TOFH2 approximate to 5.1 x 10(3) s(-1)) are measured, respectively. We demonstrate that this binuclear NiFe catalyst is stable for hours under controlled potential electrolysis conditions.