True Nature of the Transition-Metal Carbide/Liquid Interface Determines Its Reactivity

被引：31

作者：

Griesser, Christoph ^{[1
]}

Li, Haobo ^{[2
]}

Wernig, Eva-Maria ^{[1
]}

Winkler, Daniel ^{[1
]}

Nia, Niusha Shakibi ^{[1
]}

Mairegger, Thomas ^{[1
]}

Goetsch, Thomas ^{[1
,3
,4
]}

Schachinger, Thomas ^{[5
]}

Steiger-Thirsfeld, Andreas ^{[5
]}

Penner, Simon ^{[1
]}

Wielend, Dominik ^{[6
]}

Egger, David ^{[2
,7
]}

Scheurer, Christoph ^{[2
,7
]}

Reuter, Karsten ^{[2
,7
]}

Kunze-Liebhaeuser, Julia ^{[1
]}

机构：

[1] Univ Innsbruck, Dept Phys Chem, A-6020 Innsbruck, Austria

[2] Tech Univ Munich, Chair Theoret Chem & Catalysis Res Ctr, D-85748 Garching, Germany

[3] Max Planck Inst Chem Energy Convers, Dept Heterogeneous React, D-45470 Mulheim, Germany

[4] Fritz Haber Inst Max Planck Gesell, Dept Inorgan Chem, D-14195 Berlin, Germany

[5] TU Wien, Univ Serv Ctr Transmiss Electron Microscopy, A-1040 Vienna, Austria

[6] Johannes Kepler Univ Linz, Linz Inst Organ Solar Cells LIOS, Inst Phys Chem, A-4040 Linz, Austria

[7] Fritz Haber Inst Max Planck Gesell, D-14195 Berlin, Germany

来源：

ACS CATALYSIS | 2021年 / 11卷 / 08期

基金：

奥地利科学基金会;

关键词：

electrocatalysis; transition-metal carbides; electrochemical CO2 reduction; surface Pourbaix diagram; ab initio thermodynamics; solid/liquid interface; XPS; HER; CO2; ELECTROREDUCTION; TUNGSTEN CARBIDE; MOLYBDENUM; HYDROGENATION; ELECTRODES; CONVERSION; OXIDATION; PLATINUM; SURFACES; WATER;

D O I：

10.1021/acscatal.1c00415

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：

Compound materials, such as transition-metal (TM) carbides, are anticipated to be effective electrocatalysts for the carbon dioxide reduction reaction (CO2RR) to useful chemicals. This expectation is nurtured by density functional theory (DFT) predictions of a break of key adsorption energy scaling relations that limit CO2RR at parent TMs. Here, we evaluate these prospects for hexagonal Mo2C in aqueous electrolytes in a multimethod experiment and theory approach. We find that surface oxide formation completely suppresses the CO2 activation. The oxides are stable down to potentials as low as -1.9 V versus the standard hydrogen electrode, and solely the hydrogen evolution reaction (HER) is found to be active. This generally points to the absolute imperative of recognizing the true interface establishing under operando conditions in computational screening of catalyst materials. When protected from ambient air and used in nonaqueous electrolyte, Mo2C indeed shows CO2RR activity.

引用

页码：4920 / 4928

页数：9

共 49 条

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