B atom dopant-manipulate electronic structure of CuIn nanoalloy delivering wide potential activity over electrochemical CO2RR

doi:10.1016/S1872-2067(23)64443-2

Abstract

Abstract:

The accuracy and efficiency tuning the local electronic structure of catalyst active sites are pre-requisites for achieving high selectivity CO₂ reduction reaction on a wide potential window, whereas remain a great challenge. Here, a B-doped CuIn alloy catalyst with tunable electronic structure for the highly effective electrochemical conversion of CO₂ to CO has been exploited. The obtained B-doped CuIn alloy performs an optimal CO Faraday efficiency of 99% at -0.6 V (vs. the reversible hydrogen electrode) and particularly keeps outstanding CO Faraday efficiency (> 90%) over a wide cathodic electrochemical window (400 mV). Density functional theory theoretical calculation manifests that the enhanced performance is primarily ascribed to the electron-capturing ability of high valence state B atom, which optimizes the local electronic structure of adjacent metal active sites and adjusts the binding energy between catalyst and intermediates. A foundation of designing advanced electrochemical CO₂ reduction reaction catalysts can be served by the insights gained though this research.

Key words: CO₂ reduction, Wide potential window, High selectivity, B doping, Electronic structure

Jiao Wang, Fangfang Zhu, Biyi Chen, Shuang Deng, Bochen Hu, Hong Liu, Meng Wu, Jinhui Hao, Longhua Li, Weidong Shi. B atom dopant-manipulate electronic structure of CuIn nanoalloy delivering wide potential activity over electrochemical CO₂RR[J]. Chinese Journal of Catalysis, 2023, 49: 132-140.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64443-2

https://www.cjcatal.com/EN/Y2023/V49/I6/132

Figures/Tables 5

Fig. 1. (a) Schematic synthesis process of CuIn(B), Cu(B), In(B) and CuIn catalysts. Morphology and structure characterizations of CuIn(B). (b) FESEM and the average size distribution; TEM (c), HRTEM (d), HAADF-STEM (e) and EDS diagrams of elements (f?i).

Fig. 2. (a) XRD of CuIn(B) and CuIn; (b) XPS spectra of B 1s; (c) Auger Cu LMM; (d) Cu 2p; (e) In 3d.

Fig. 3. Electrocatalytic CO2RR performances of CuIn(B). (a) LSV curves tested in 0.5 mol/L KHCO3 solution with saturated Ar or CO2. (b) FE of gas products of CuIn(B). (c) FECO obtained within the scope of -0.5 V to -1.2 V (vs. RHE). (d) jCO obtained at different applied potential. (e) EECO of diverse catalysts. (f) Long-term durability test of CuIn(B) at -0.8 V (vs. RHE). The standard deviation of three separate measurements of the same sample is represented by the error estimates.

Fig. 4. (a) Differences in current density (Δj/2) displayed against scan rates. (b) The surface roughness factor. (c) Nyquist curves. (d) Tafel curves.

Fig. 5. Theoretical calculations on CuIn(B) and CuIn. (a) Calculated free energy diagrams on the CuIn(B) and CuIn. (b) The distinction in thermodynamic limiting potentials for CO2-to-CO conversion and HER on catalysts. (c) The top and side view of charge density difference in CuIn(B), where charge consumption and accumulation were described by cyan and yellow, respectively. (d) PDOS curves of Cu 3d, In 3d, the Cu site adsorbed with *COOH intermediate on the CuIn(B) and CuIn. The dashed orange line manifests the Fermi level (Ef). Dotted grey lines represent the d-band centers (Ed).

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B atom dopant-manipulate electronic structure of CuIn nanoalloy delivering wide potential activity over electrochemical CO₂RR

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