Product-Specific Active Site Motifs of Cu for Electrochemical CO2 Reduction
Journal
Chem
Journal Volume
7
Journal Issue
2
Pages
406-420
Date Issued
2021
Author(s)
Zhu C
Abstract
Electrochemical CO2 reduction (CO2R) to fuels is a promising route to close the anthropogenic carbon cycle and store renewable energy. Cu is the only metal catalyst that produces C2+ fuels, yet challenges remain in the improvement of electrosynthesis pathways for highly selective fuel production. To achieve this, mechanistically understanding CO2R on Cu, particularly identifying the product-specific active sites, is crucial. We rationally designed and fabricated nine large-area single-crystal Cu foils with various surface orientations as electrocatalysts and monitored their surface reconstructions using operando grazing incidence X-ray diffraction (GIXRD) and electron back-scattered diffraction (EBSD). We quantitatively established correlations between the Cu atomic configurations and the selectivities toward multiple products and provide a paradigm to understand the structure-function correlation in catalysis. ? 2020 Elsevier Inc.Aqueous electrochemical CO2 reduction (CO2R) on Cu can generate a variety of valuable fuels, yet challenges remain in the improvement of electrosynthesis pathways for highly selective fuel production. Mechanistically, understanding CO2R on Cu, particularly identifying the product-specific active sites, is crucial. Herein, we rationally designed and fabricated nine large-area single-crystal Cu foils with various surface orientations as electrocatalysts and identified the voltage- and facet-dependent CO2R selectivities. Operando grazing incidence X-ray diffraction (GIXRD) and electron back-scattered diffraction (EBSD) were applied to track the top-surface reconstructions of Cu, and we correlate the structural evolution with the change of product selectivities. We extracted three distinct structural descriptors, including crystal facet, atomic coordination number, and step-terrace angle, to reveal the intrinsic structure-function relationships and uniquely identify the specific product-producing sites for CO2R. Our work guides the rational design of Cu-based CO2R electrocatalysts and, more importantly, establishes a paradigm to understand the structure-function correlation in catalysis. ? 2020 Elsevier Inc.We rationally designed and fabricated nine large-area single-crystal Cu foils with various orientations as electrocatalysts and operandoly monitored their surface reconstructions. Quantitative correlations between Cu atomic configurations and the selectivities toward multiple products were established. We extracted three distinct structural descriptors, including crystal facet, atomic coordination number, and step-terrace angle, to reveal the intrinsic structure-function relationships and uniquely identify the specific product-producing sites of Cu for CO2R. ? 2020 Elsevier Inc.
Subjects
active site motifs; CO2 reduction; electrochemistry; operando GIXRD; SDG11: Sustainable cities and communities; single-crystal Cu; surface reconstruction
Type
journal article