Grain boundary-abundant copper nanoribbons on balanced gas-liquid diffusion electrodes for efficient CO2 electroreduction to C2H4

doi:10.1016/S1872-2067(23)64540-1

Abstract

Abstract:

The electrocatalytic CO₂ reduction reaction (CO₂RR) is a promising technology to produce value-added hydrocarbon chemicals, however, achieving a high selectivity to C₂₊ products at the industrial current density remains a great challenge. Herein, we demonstrate grain boundary-abundant copper (Cu) nanoribbons on balanced gas-liquid diffusion electrodes for efficient CO₂RR to ethylene (C₂H₄). The Cu(II) carbonate basic (Cu₂CO₃(OH)₂) nanoribbon is used as a precursor to convert into metal Cu under in situ electrochemical reduction. Unexpectedly, the generated Cu nanoribbon is formed by stacking tiny nanoparticles with exposure of Cu(111), Cu(200) and Cu(220) facets, which creates abundant grain boundaries (GBs). During CO₂RR test, the thickness of the catalyst layer is identified as a crucial factor for the mass transfer of CO₂ and electrolyte. By tailoring the thickness of catalytic layer, CO₂ and electrolyte can simultaneously reach the surface of catalyst and participate in CO₂RR. Under the synergetic effects of GBs and balanced gas-liquid diffusion, the optimized electrode delivers the Faradaic efficiencies toward C₂H₄ and C₂₊ products as high as 67.2% and 82.1% at the current density of 700 mA cm^-2, respectively. Moreover, the partial current density of C₂H₄ can reach up to 505 mA cm^-2, which is significantly higher than most reported results. The in situ Raman and attenuated total reflection surface-enhanced infrared absorption spectra show that abundant GBs enhance the activation of CO₂ and significantly promote the formation and adsorption of *CO intermediates, which accelerate C-C coupling to form *OCCO and *OCCOH intermediates and improve the production of C₂H₄ and other C₂₊ products.

Key words: Electrochemical CO₂ reduction, Ethylene, C₂₊ product, Grain boundary, Gas-liquid diffusion

Lei Bian, Zi-Yang Zhang, Hao Tian, Na-Na Tian, Zhi Ma, Zhong-Li Wang. Grain boundary-abundant copper nanoribbons on balanced gas-liquid diffusion electrodes for efficient CO₂ electroreduction to C₂H₄[J]. Chinese Journal of Catalysis, 2023, 54: 199-211.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64540-1

https://www.cjcatal.com/EN/Y2023/V54/I11/199

Figures/Tables 6

Fig. 1. (a) Schematic illustration for the preparation of the Cu2CO3(OH)2 and ED-Cu nanoribbons catalysts. SEM images of (b) Cu2CO3(OH)2 precursor and (c) ED-Cu catalyst. (d) TEM images of ED-Cu. (e,f) HR-TEM image of ED-Cu nanoribbon. Inset in (e) and (f) is the corresponding FFT pattern.

Fig. 2. Characterization of chemical components of catalysts. (a) XRD patterns, (b) Cu 2p XPS spectra, (c) Cu LMM spectra, and (d) C 1s XPS spectra of Cu2CO3(OH)2 precursor before reduction and ED-Cu catalyst after reduction. (e) Cu K-edge XANES spectra and (f) Cu K-edge Fourier transformed EXAFS spectra of ED-Cu catalyst..

Fig. 3. (a) Cross-section SEM images of the electrodes with different catalytic layer thicknesses. (b) Current density, (c) C2H4 and (d) H2 FEs of different electrodes. (e) Schematic illustration of gas-liquid diffusion and reaction interface on electrodes with different catalyst layer thicknesses (CL) during CO2RR reaction process.

Fig. 4. CO2RR performance on ED-Cu, OD-Cu and TR-Cu catalysts. (a) LSV curves of different catalysts. Product distributions and corresponding Fes produced by (b) ED-Cu, (c) OD-Cu and (d) TR-Cu. (e) FEs of C2+ and (f) partial current density of C2H4 over ED-Cu, OD-Cu and TR-Cu at different current densities. (g) Comparisons of the FE and current density of C2H4 for CO2RR on ED-Cu with those of reported Cu-based catalysts. (h) Stability test of graphite/carbon NPs/ED-Cu/PTFE electrode at a constant current density of 700 mA cm-2 in a flow cell with 1 mol L-1 KOH.

Fig. 5. In situ Raman spectra of CO2RR in the regions of 200-1400 and 1600-2500 cm-1 on (a) ED-Cu, (b) OD-Cu, and (c) TR-Cu.

Fig. 6. In situ ATR-SEIRAS spectra of catalysts under CO2RR and reaction mechanism. (a) ED-Cu. (b) OD-Cu. (c) TR-Cu. (d) Schematic diagram of the proposed catalytic mechanism over ED-Cu catalyst.

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Grain boundary-abundant copper nanoribbons on balanced gas-liquid diffusion electrodes for efficient CO₂ electroreduction to C₂H₄

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