Tuning the intermediate reaction barriers by a CuPd catalyst to improve the selectivity of CO2 electroreduction to C2 products

doi:10.1016/S1872-2067(20)63754-8

Abstract

Abstract:

Electrochemical CO₂ reduction is a promising strategy for the utilization of CO₂ and intermittent excess electricity. Cu is the only single metal catalyst that can electrochemically convert CO₂ into multicarbon products. However, Cu exhibits an unfavorable activity and selectivity for the generation of C2 products because of the insufficient amount of CO* provided for the C-C coupling. Based on the strong CO₂ adsorption and ultrafast reaction kinetics of CO* formation on Pd, an intimate CuPd(100) interface was designed to lower the intermediate reaction barriers and improve the efficiency of C2 product formation. Density functional theory (DFT) calculations showed that the CuPd(100) interface enhanced the CO₂ adsorption and decreased the CO₂* hydrogenation energy barrier, which was beneficial for the C-C coupling. The potential-determining step (PDS) barrier of CO₂ to C2 products on the CuPd(100) interface was 0.61 eV, which was lower than that on Cu(100) (0.72 eV). Encouraged by the DFT calculation results, the CuPd(100) interface catalyst was prepared by a facile chemical solution method and characterized by transmission electron microscopy. CO₂ temperature-programmed desorption and gas sensor experiments further confirmed the enhancement of the CO₂ adsorption and CO₂* hydrogenation ability of the CuPd(100) interface catalyst. Specifically, the obtained CuPd(100) interface catalyst exhibited a C2 Faradaic efficiency of 50.3% ± 1.2% at ‒1.4 V_RHE in 0.1 M KHCO₃, which was 2.1 times higher than that of the Cu catalyst (23.6% ± 1.5%). This study provides the basis for the rational design of Cu-based electrocatalysts for the generation of multicarbon products by fine-tuning the intermediate reaction barriers.

Key words: Carbon dioxide reduction, C2 products, Electrocatalyst, Copper-palladium interface, Intermediate reaction barriers

Li Zhu, Yiyang Lin, Kang Liu, Emiliano Cortés, Hongmei Li, Junhua Hu, Akira Yamaguchi, Xiaoliang Liu, Masahiro Miyauchi, Junwei Fu, Min Liu. Tuning the intermediate reaction barriers by a CuPd catalyst to improve the selectivity of CO₂ electroreduction to C2 products[J]. Chinese Journal of Catalysis, 2021, 42(9): 1500-1508.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63754-8

https://www.cjcatal.com/EN/Y2021/V42/I9/1500

Figures/Tables 5

Fig. 1. (a) Adsorption energy of CO2 and ΔG of CO2* hydrogenation; (b) Calculated free energy diagrams for the CO2 reduction process; (c) Schematic diagram of the PDS of the CO2 reduction process on Cu(100), CuPd(100) interface, and Pd(100) facet.

Fig. 2. (a) XRD patterns of the prepared Cu, CuPd, and Pd samples after electrochemical reduction for 30 min; (b,c) Low-resolution and high-resolution TEM images of the CuPd sample; (d) HAADF-STEM image combined with the EDS mapping of the CuPd sample.

Fig. 3. XPS spectra of Cu 2p (a) and Pd 3d (b); EXAFS spectra of Cu K-edge (c) and Pd K-edge (d) of the CuPd sample.

Fig. 4. CO2-TPD (a) and CO-TPD (b) curves of Cu, CuPd(100) interface, and Pd catalysts; (c) Gas sensor experiments for Cu, CuPd(100) interface, and Pd catalysts at 0.1, 0.2, 0.3, 0.4, and 0.5 V; (d) Calculated current density differences (Δj) between vacuum and CO2+H2O atmosphere.

Fig. 5. (a) FE of different products for Cu, CuPd(100) interface, and Pd catalysts at different applied potentials; (b) FE ratios of C2 to C1 products (FEC2/FEC1) at different applied potentials; (c) Current density curves and (d) Tafel slopes for Cu, CuPd(100) interface, and Pd catalysts.

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Tuning the intermediate reaction barriers by a CuPd catalyst to improve the selectivity of CO₂ electroreduction to C2 products

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