Core–shell nanoporous AuCu3@Au monolithic electrode for efficient electrochemical CO2 reduction

Published on Feb 11, 2020in Journal of materials chemistry. A, Materials for energy and sustainability11.301
· DOI :10.1039/C9TA09471G
Xiaoming Ma3
Estimated H-index: 3
(Tianjin University of Technology),
Yongli Shen9
Estimated H-index: 9
(Tianjin University of Technology)
+ 6 AuthorsChanghua An23
Estimated H-index: 23
(Tianjin University of Technology)
Selective conversion of carbon dioxide (CO2) to a reusable form of carbon via electrochemical reduction has attracted intensive interest for the storage of renewable energy. However, the achievement of efficient bulk monolithic electrocatalysts still remains a challenge. Herein, a facile oxidative etching of the Au20Cu80 alloy was developed for the synthesis of a monolithic nanoporous core–shell structured AuCu3@Au electrode, which showed a faradaic efficiency (FE) of 97.27% with a partial current density of 5.3 mA cm−2 at −0.6 V vs. RHE for the production of CO. The FE value is about 1.45 times higher than that over the Au nanocatalyst. Unlike single nanoporous Au, AuCu3@Au maintained an excellent performance in a broad potential window. Furthermore, a 23 cm long nanoporous AuCu3@Au bulk electrode with good ductility was prepared, over which the active current reached up to 37.2 mA with a current density of 10.78 mA cm−2 at −0.7 V vs. RHE, pushing the reduction of CO2 to industrialization. The unsaturated coordination environment with a coordination number of 8.2 over the shell gold and curved interface determined this high electrocatalytic performance. Density functional theory calculations suggested that the double-dentate adsorption structure in the AuCu3@Au catalyst effectively improves the stability of the *COOH intermediate. The density of states indicates that the introduction of Cu causes the d-band-centre of AuCu3@Au to move toward the Fermi level, directly bonding with *COOH. Therefore, the adsorption of *COOH on the surface of the AuCu3@Au catalyst is strengthened, facilitating the formation of CO. This work opens an avenue to achieve self-supported porous electrodes for various useful catalytic conversions.
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This work was supported by Competitive Research Grant (URF/1/2985-01-01) from King Abdullah University of Science and Technology. The authors thank Dr. Srikanth Pedireddy for generating Scheme 1, Figure S4 (Supporting Information), and ToC. Additionally, the authors acknowledge Hyun Ho Hwang (Heno) at the Office of Academic Writing Services at KAUST for generating Figure 2 in the manuscript.
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