Adequately stabilized and exposed copper heterostructure for CO2 electroreduction to ethanol with ultrahigh mass activity

doi:10.1016/S1872-2067(23)64604-2

Abstract

Abstract:

Adequately exposure of active sites to reactants is crucial in improving the actual catalytic activity in various electrocatalytic reactions. e.g., CO₂ electroreduction. Herein, we construct abundant opening mesopores throughout carbon nanofibers via a simple O₂ plasma treatment, which can simultaneously create a CO₂-rich environment and expose Cu/Cu_xO sites to the reaction interface. The unique Cu/Cu_xO sites can generate a 70.7% Faradaic efficiency of C₂H₅OH at the 400 mA cm^-2 current density. Moreover, this superior structure can significantly increase the number of active sites that actually participated in the reaction, and leads to an exceptional 8.4 A mg^-1 Cu mass activity for C₂H₅OH, which is among the highest mass activity for C₂H₅OH ever reported. The DFT calculation and CO-TPD studies reveal that the created Cu/Cu_xO heterostructure provides adequate *CO coverages and lowers the energy barrier of the C-C coupling process for ethanol formation, in which the key ethanol intermediates are detected via the in-situ spectra investigations. This strategy can be easily applied to construct efficient catalysts in other electrocatalytic reactions.

Key words: CO₂ electroreduction, Copper heterostructure, Opening mesopores, Mass activity, Ethanol

Xingxing Jiang, Yuxin Zhao, Yan Kong, Jianju Sun, Shangzhao Feng, Qi Hu, Hengpan Yang, Chuanxin He. Adequately stabilized and exposed copper heterostructure for CO₂ electroreduction to ethanol with ultrahigh mass activity[J]. Chinese Journal of Catalysis, 2024, 58: 216-225.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64604-2

https://www.cjcatal.com/EN/Y2024/V58/I3/216

Figures/Tables 6

Fig. 1. Production process of Cu-PCNF@O2 via electrospinning and O2 plasma techniques.

Fig. 2. (a) The flexibility tests of Cu-PCNF@O2. Morphological and structural characterization of Cu-PCNF@O2: SEM image (b), TEM images (c,d), HR-TEM image (e), HAADF-STEM image and EDS elemental mappings of C, O, Cu (f).

Fig. 3. XRD patterns (a) and Raman spectra (b) of four samples. (c) N2 adsorption-desorption isotherms curve of Cu-PCNF@O2, insert the related pore size distribution. Survey XPS (d), comparison fitting curves of Cu 2p XPS spectra (e) and Cu LM2 Auger spectra (f) for Cu-CNF, Cu-PCNF, Cu-PCNF@N2 and Cu-PCNF@O2. (g) EPR Spectroscopy of Cu-PCNF and Cu-PCNF@O2. (h) Valence band spectra of Cu-PCNF and Cu-PCNF@O2.

Fig. 4. (a) LSV curves comparison of four samples in CO2-saturated 0.5 mol L?1 KHCO3 electrolyte. (b) Faradaic efficiencies for CO2RR products on Cu-PCNF@O2 at various potentials. C2H5OH partial current densities (c) and C2/C1 products ratios (d) in H-type cell of three samples. C2H5OH Faradaic efficiencies (e) and Cu mass activity (f) of three samples in 1 mol L?1 KOH electrolyte using a flow cell. (g) CO2RR to ethanol performance comparisons of Cu-PCNF@O2 in this work with other reported Cu-based catalysts. (h) Long-term CO2RR performance on Cu-PCNF@O2 at 300 mA cm-2 in 1 mol L?1 KOH.

Fig. 5. Negative charge density distribution on the Simulated Cu-CNF (a), Cu-PCNF (b) and Cu-PCNF@O2 (c) surface. Surface K+ density distribution on the simulated Cu-CNF (d), Cu-PCNF (e) and Cu-PCNF@O2 (f) surface.

Fig. 6. (a,b) In-situ FTIR spectra for CO2RR on Cu-PCNF@O2 from OCP ~?1.2 VRHE. (c) The adsorption energies of *CO and *OCCO on different sites of Cu-PCNF@O2. (d) CO-TPD spectra of Cu-PCNF and Cu-PCNF@O2. (e) Free energy for different pathways of *CO to form C?C coupling intermediate *OCCHO on Cu/CuxO heterostructure surface. (f) Energy diagram of CO2 reduction to *OCCHO on Cu and Cu/CuxO heterostructure surface. (g) Schematic illustration of a plausible CO2RR mechanism to form C2H5OH.

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Adequately stabilized and exposed copper heterostructure for CO₂ electroreduction to ethanol with ultrahigh mass activity

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