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Urea-Based Multipoint Hydrogen-Bond Donor Additive Promotes Electrochemical CO2 Reduction Catalyzed by Nickel Cyclam
Organometallics ( IF 2.5 ) Pub Date : 2018-07-03 , DOI: 10.1021/acs.organomet.8b00308 Eva M. Nichols 1 , Christopher J. Chang 1
Organometallics ( IF 2.5 ) Pub Date : 2018-07-03 , DOI: 10.1021/acs.organomet.8b00308 Eva M. Nichols 1 , Christopher J. Chang 1
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We report that a urea-based multipoint hydrogen-bond donor additive leads to an enhancement in activity for electrochemical CO2 reduction to CO catalyzed by Ni cyclam without altering this catalyst’s high selectivity for CO2 versus proton reduction. Comparison of peak catalytic currents in the presence of a bis(aryl)urea additive versus an isostructural amide as a one-point hydrogen-bond counterpart, as well as other weakly coordinating acids with comparable pKa values, reveals that the urea preferentially augments CO2 electrocatalysis. This observation suggests that the ability of the urea to form cooperative hydrogen-bond interactions is critical for the observed increases in activity rather than its acidity alone. Indeed, the boost in catalytic activity is observed in acetonitrile electrolyte containing up to 1 M water, indicating the organourea’s role as a cocatalyst rather than a stoichiometric additive. This work establishes a starting point for applying principles of organocatalysis to electrocatalysis, where rational design and implementation of organic additives to electrocatalytic platforms can be a promising avenue to enhance activity and/or control product selectivity without requiring elaborate ligand synthesis.
中文翻译：
尿素基多点氢键供体添加剂促进镍基环己酰胺催化电化学还原CO 2
我们报告说，基于尿素的多点氢键供体添加剂导致Ni Cyclam催化电化学CO 2还原成CO的活性增强，而不会改变该催化剂对质子还原的高CO 2选择性。在双（芳基）脲添加剂与同构酰胺作为单点氢键对应物以及其他具有相当的p K a值的弱配位酸存在下，峰值催化电流的比较表明，尿素优先增加一氧化碳2电催化。该观察结果表明，尿素形成协同氢键相互作用的能力对于观察到的活性增加而不是仅其酸度增加至关重要。实际上，在含水量高达1 M的乙腈电解质中观察到了催化活性的增强，表明有机脲作为助催化剂而不是化学计量添加剂的作用。这项工作为将有机催化原理应用到电催化建立了一个起点，在此方法中，有机添加剂在电催化平台上的合理设计和实施可以成为增强活性和/或控制产物选择性而无需复杂配体合成的有前途的途径。
更新日期：2019-02-06
中文翻译：
尿素基多点氢键供体添加剂促进镍基环己酰胺催化电化学还原CO 2
我们报告说，基于尿素的多点氢键供体添加剂导致Ni Cyclam催化电化学CO 2还原成CO的活性增强，而不会改变该催化剂对质子还原的高CO 2选择性。在双（芳基）脲添加剂与同构酰胺作为单点氢键对应物以及其他具有相当的p K a值的弱配位酸存在下，峰值催化电流的比较表明，尿素优先增加一氧化碳2电催化。该观察结果表明，尿素形成协同氢键相互作用的能力对于观察到的活性增加而不是仅其酸度增加至关重要。实际上，在含水量高达1 M的乙腈电解质中观察到了催化活性的增强，表明有机脲作为助催化剂而不是化学计量添加剂的作用。这项工作为将有机催化原理应用到电催化建立了一个起点，在此方法中，有机添加剂在电催化平台上的合理设计和实施可以成为增强活性和/或控制产物选择性而无需复杂配体合成的有前途的途径。
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