CO2-to-methanol electroconversion on a molecular cobalt catalyst facilitated by acidic cations

被引：40

作者：

Yu, Sunmoon ^{[1
]}

Yamauchi, Hiroki ^{[2
]}

Wang, Shuo ^{[1
,3
]}

Aggarwal, Abhishek ^{[1
,3
]}

Kim, Junghwa ^{[1
,3
]}

Gordiz, Kiarash ^{[4
]}

Huang, Botao ^{[1
]}

Xu, Hongbin ^{[1
,3
]}

Zheng, Daniel J. ^{[1
,3
]}

Wang, Xiao ^{[1
,5
]}

Iriawan, Haldrian ^{[1
,3
]}

Menga, Davide ^{[1
]}

Shao-Horn, Yang ^{[1
,3
,4
]}

机构：

[1] MIT, Res Lab Elect, Cambridge, MA 02139 USA

[2] Niterra Co Ltd, Sci Res Lab, Iwasaki, Japan

[3] MIT, Dept Mat Sci & Engn, Cambridge, MA 02139 USA

[4] MIT, Dept Mech Engn, Cambridge, MA 02139 USA

[5] MIT, Dept Chem Engn, Cambridge, MA USA

来源：

NATURE CATALYSIS | 2024年 / 7卷 / 09期

基金：

美国国家科学基金会;

关键词：

ELECTROCHEMICAL REDUCTION; CARBON-DIOXIDE; FORCE-FIELD; CO2; DYNAMICS; PH; SELECTIVITY;

D O I：

10.1038/s41929-024-01197-2

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The crucial role of electrolyte cations in CO2 electroreduction has received intensive attention. One prevailing theory is that through electrostatic interactions or direct coordination, larger cations such as Cs+ can better stabilize the key intermediate species for CO and multicarbon (C2+) product generation, for example, on silver and copper, respectively. Here we show that smaller, more acidic alkali metal cations greatly enhance CO2-to-methanol conversion kinetics (Li+ > Na+ > K+ > Cs+) on an immobilized molecular cobalt catalyst, unlike the trend observed for CO and C2+. Through electrokinetic analyses and kinetic isotope effect studies along with computational investigations, we show that the hydration shell of a cation serves as a proton donor in the rate-determining protonation step of adsorbed CHO where acidic cations promote the proton-coupled electron transfer. This study reveals the promotional effect of cation solvation environment on CO2 electroreduction beyond the widely acknowledged stabilizing effect of cations.

引用

页码：1000 / 1009

页数：10

共 65 条

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