Complementary Operando Spectroscopy Identification of In-situ Generated Metastable Charge-asymmetry Cu-CuN Clusters for CO Reduction to Ethanol

Overview

Journal Nat Commun

Specialty Biology

Date 2022 Mar 12

PMID 35277523

Authors

Xiaozhi Su

Zhuoli Jiang

Jing Zhou

Hengjie Liu

Danni Zhou

Huishan Shang

Xingming Ni

Zheng Peng

Fan Yang

Wenxing Chen

Zeming Qi

Dingsheng Wang

Yu Wang

Affiliations

Soon will be listed here.

Abstract

Copper-based materials can reliably convert carbon dioxide into multi-carbon products but they suffer from poor activity and product selectivity. The atomic structure-activity relationship of electrocatalysts for the selectivity is controversial due to the lacking of systemic multiple dimensions for operando condition study. Herein, we synthesized high-performance CORR catalyst comprising of CuO clusters supported on N-doped carbon nanosheets, which exhibited high C products Faradaic efficiency of 73% including decent ethanol selectivity of 51% with a partial current density of 14.4 mA/cm at -1.1 V vs. RHE. We evidenced catalyst restructuring and tracked the variation of the active states under reaction conditions, presenting the atomic structure-activity relationship of this catalyst. Operando XAS, XANES simulations and Quasi-in-situ XPS analyses identified a reversible potential-dependent transformation from dispersed CuO clusters to Cu-CuN clusters which are the optimal sites. This cluster can't exist without the applied potential. The N-doping dispersed the reduced Cu clusters uniformly and maintained excellent stability and high activity with adjusting the charge distribution between the Cu atoms and N-doped carbon interface. By combining Operando FTIR and DFT calculations, it was recognized that the Cu-CuN clusters displayed charge-asymmetric sites which were intensified by CH adsorbing, beneficial to the formation of the high-efficiency asymmetric ethanol.

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