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. 2023 Oct 5;14(1):6142.
doi: 10.1038/s41467-023-41871-w.

Cascade electrocatalysis via AgCu single-atom alloy and Ag nanoparticles in CO2 electroreduction toward multicarbon products

Cheng Du #  1 , Joel P Mills #  1 , Asfaw G Yohannes #  2 , Wei Wei #  1 , Lei Wang  1 , Siyan Lu  1 , Jian-Xiang Lian  2 , Maoyu Wang  3 , Tao Guo  1 , Xiyang Wang  1 , Hua Zhou  3 , Cheng-Jun Sun  3 , John Z Wen  1 , Brian Kendall  4 , Martin Couillard  5 , Hongsheng Guo  5 , ZhongChao Tan  6 , Samira Siahrostami  7 , Yimin A Wu  8   9   10
Affiliations

Cascade electrocatalysis via AgCu single-atom alloy and Ag nanoparticles in CO2 electroreduction toward multicarbon products

Cheng Du et al. Nat Commun. .

Abstract

Electrocatalytic CO2 reduction into value-added multicarbon products offers a means to close the anthropogenic carbon cycle using renewable electricity. However, the unsatisfactory catalytic selectivity for multicarbon products severely hinders the practical application of this technology. In this paper, we report a cascade AgCu single-atom and nanoparticle electrocatalyst, in which Ag nanoparticles produce CO and AgCu single-atom alloys promote C-C coupling kinetics. As a result, a Faradaic efficiency (FE) of 94 ± 4% toward multicarbon products is achieved with the as-prepared AgCu single-atom and nanoparticle catalyst under ~720 mA cm-2 working current density at -0.65 V in a flow cell with alkaline electrolyte. Density functional theory calculations further demonstrate that the high multicarbon product selectivity results from cooperation between AgCu single-atom alloys and Ag nanoparticles, wherein the Ag single-atom doping of Cu nanoparticles increases the adsorption energy of *CO on Cu sites due to the asymmetric bonding of the Cu atom to the adjacent Ag atom with a compressive strain.

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Conflict of interest statement

The authors declare the following competing interests: Y.A.W., C.D., J.P.M., and H.G. have filed a patent application through the University of Waterloo on this technology related to this CuAg single atom alloy for the electrocatalytic CO2 reduction processes (US Patent application number 63/473,924). The remaining authors declare no competing interests.

Figures

Fig. 1
Fig. 1. Scanning transmission electron microscopy imaging of catalysts.
A Scheme of the synthesis process of AgCu catalysts; B BF-STEM image of AgCu SANP; C HAADF-STEM image of AgCu SANP; D AC-HAADF-STEM image of AgCu SANP; E STEM and EDX element mapping images of AgCu SANP.
Fig. 2
Fig. 2. X-ray diffraction and spectroscopies characterization of catalysts.
A XRD spectra, B Ag 3d core-level XPS spectra, C Cu 2p core-level XPS spectra of Cu NP, AgCu SAA, AgCu SANP, and AgCu NP; D Ag K-edge XANES spectra of AgCu SANP and Ag foil; E Ag K-edge XAFS experimental and fitting spectrum of AgCu SANP; F Scheme of AgCu SANP structure and the ratio of Ag-Cu and Ag-Ag contribution from fitting results. Source data are provided as a Source Data file.
Fig. 3
Fig. 3. Electrocatalytic CO2 reduction and CO reduction performance of the catalysts.
A Scheme of the cascade catalysis mechanism over AgCu SANP; B FE results of Cu NP, AgCu SAA, AgCu SANP, and Ag NP catalysts toward CO2RR at −0.65 V; C Total current density of Cu NP, AgCu SAA, AgCu SANP, and Ag NP catalysts at −0.65 V; D Performances comparison of AgCu SANP and reported results; E FE results of Cu NP, AgCu SAA, and AgCu SANP toward CO reduction at −0.65 V; F Long-term stability results of AgCu SANP toward CO2RR; G FE results of AgCu SANP toward CO2RR feeding with different CO2 concentrations. Note that the FE of H2 products from competitive hydrogen evolution reaction was not quantified. All the error bars are obtained from three independent experiments. Source data are provided as a Source Data file.
Fig. 4
Fig. 4. Mechanistic studies by the density functional theory calculations.
Mechanistic studies by the density functional theory calculations. A Comparison of the C-C coupling activation barrier for the *CHO (on CuAg and pure Cu) and *COH intermediates (CuAg); B The lowest free energy pathway for the formation of ethanol (orange), ethylene (blue) and acetic acid (magenta) on CuAg and C the associated chemical formula for each elementary step in (B). Source data are provided as a Source Data file.
See this image and copyright information in PMC

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