化学
路易斯酸
电化学
配体(生物化学)
铜
动能
金属
配位复合体
极性效应
电子效应
结晶学
无机化学
计算化学
立体化学
催化作用
物理化学
药物化学
电极
有机化学
受体
物理
量子力学
生物化学
作者
Walter D. Johnsen,Mawuli Deegbey,David C. Grills,Dmitry E. Polyansky,Karen I. Goldberg,Elena Jakubı́ková,Thomas E. Mallouk
标识
DOI:10.1021/acs.inorgchem.3c01003
摘要
A series of dinuclear molecular copper complexes were prepared and used to model the binding and Lewis acid stabilization of CO in heterogeneous copper CO2 reduction electrocatalysts. Experimental studies (including measurement of rate and equilibrium constants) and electronic structure calculations suggest that the key kinetic barrier for CO binding may be a σ-interaction between CuI and the incoming CO ligand. The rate of CO coordination can be increased upon the addition of Lewis acids or electron-withdrawing substituents on the ligand backbone. Conversely, Keq for CO coordination can be increased by adding electron density to the metal centers of the compound, consistent with stronger π-backbonding. Finally, the electrochemically measured kinetic results were mapped onto an electrochemical zone diagram to illustrate how these system changes enabled access to each zone.
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