Hybrid Organic‐Inorganic Heterogeneous Interfaces for Electrocatalysis: A Theoretical Study of CO 2 Reduction to C 2
Hybrid Organic‐Inorganic Heterogeneous Interfaces for Electrocatalysis: A Theoretical Study of CO 2 Reduction to C 2
复制标题
用于电催化的有机-无机杂化多相界面：CO 2 还原为 C 2 的理论研究
DOI：
10.1002/cctc.202101224
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发表时间：
2021
期刊：
影响因子：
4.5
通讯作者：
Che, Fanglin
中科院分区：
文献类型：
--
作者：
Wan, Mingyu;Gu, Zhiyong;Che, Fanglin
混合有机-无机非均相催化界面，传统的催化材料被自组装单层（sam）修饰，通过设计双有机-无机活性位点和诱导约束效应，创造了有前途的特性来控制广泛的催化过程。为了提供基本的见解，我们研究了co2电还原成有价值的C2化学物质（CO2RR - To - C2）。我们的理论结果表明，1/4单层氨基硫酸盐通过：(1)降低表面能抑制表面重建，提高了CO2RR - to - co2的稳定性、活性和选择性；(2)通过双有机-无机（即有机-无机）促进co2活化和C - C耦合。，−NH, Cu)活性位点；(3)通过增大CO*和COH*吸附能差的约束效应促进C - C耦合；(4)在电极/电解质界面电场作用下，诱导Cu表面局部电场，改变其偶极矩和极化率，使其有利于C - C耦合。
Hybrid organic‐inorganic heterogeneous catalytic interfaces, where traditional catalytic materials are modified with self‐assembled monolayers (SAMs), create promising features to control a wide range of catalytic processes through the design of dual organic‐inorganic active sites and the induced confinement effect. To provide a fundamental insight, we investigated CO2electroreduction into valuable C2chemicals (CO2RR‐to‐C2) over SAM‐modulated Cu. Our theoretical results show that 1/4 monolayer aminothiolates improve the stability, activity and selectivity of CO2RR‐to‐C2by: (1) decreasing surface energy to suppress surface reconstruction; (2) facilitating CO2activation and C−C coupling through dual organic‐inorganic (i. e., −NH, Cu) active sites; (3) promoting C−C coupling via confinement effects that enlarge the adsorption energy difference between CO*and COH*; (4) inducing local electric fields to Cu surface and changing its dipole moment and polarizability to be in favor of C−C coupling under electrode/electrolyte interfacial electric field.