Grain boundary density effect for highly selective C2+ production from CO2 reduction: Polycrystalline Cu electrocatalyst as a paradigm

doi:10.1016/S1872-2067(26)65187-X

Abstract

Abstract:

Grain boundaries (GBs) in Cu-based electrocatalysts have been recognized as efficient sites producing multi-carbon chemicals (C₂₊) from CO₂ reduction, yet the effective GB regulation strategy for targeted activity enhancement is still unavailable to date, and consequently their catalytic mechanism remains unclear. Herein, polycrystalline Cu catalysts (p-Cu) with varying GB densities were fabricated by electrochemical reconstruction of mesoporous Cu₂O nanocrystals with different primary particle sizes. It is discovered that increasing GB density results in correspondingly decreased coordination number (CN) of Cu sites, which in turn contributes to the progressive enhancement of C₂₊ selectivity over the p-Cu catalysts. Specifically, the determined optimal GB density of 151 μm^-1, corresponding to a Cu CN of 6.36, delivers a remarkably augmented C₂₊ Faradaic efficiency of up to 88.06% (70.55% for C₂H₄) and a C₂₊ partial current density as high as 722.7 mA cm^-2, rendering the p-Cu ranked among the best state-of-art catalysts. Mechanism explorations disclose that increased GB density leads to lowered CN Cu sites, which are responsible for the largely amplified *CO coverage together with increased *CO_atop/*CO_bridge ratio, and enhanced localized alkaline environment, thereby boosting an energy-efficient *CO-*COH coupling pathway to produce C₂₊. This work presents a facile regulation strategy of GB density in Cu catalysts, and on this basis establishes the correlation among GB density, the CN of Cu sites, and the selectivity of C₂₊ products.

Key words: Electrocatalytic CO₂ reduction reaction, Mesoporous nanocrystal, Polycrystalline Cu, Grain boundary, Coordination number, Multi-carbon chemicals

Yizhu Qiao, Xixiong Jin, Bohan A, Zixuan Wei, Min Wang, Weiren Chen, Xi Huang, Lingxia Zhang, Jianlin Shi. Grain boundary density effect for highly selective C₂₊ production from CO₂ reduction: Polycrystalline Cu electrocatalyst as a paradigm[J]. Chinese Journal of Catalysis, 2026, 89: 367-377.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65187-X

https://www.cjcatal.com/EN/Y2026/V89/I10/367

Figures/Tables 5

Fig. 1. Synthesis and characterizations of m-Cu2O and b-Cu2O. (a) Schematic illustration of the synthesis of m-Cu2O and b-Cu2O. (b) HRTEM image (inset: the corresponding SAED pattern) and (c) SEM image of m-Cu2O-3. XRD patterns (d) and N2 adsorption-desorption isotherms (inset: the BJH pore size distribution plots) (e) of m-Cu2O and b-Cu2O.

Fig. 2. CO2RR performances of m-Cu2O and b-Cu2O in a flow cell. (a) Schematic illustration of the flow-cell. (b) Current density-dependent FEs of various products over m-Cu2O-3. FEs of C2H4 (c), FEs of C2+ products (d), and partial current density of C2+ products (e) over m-Cu2O and b-Cu2O. FEs and partial current density of C2H4 (f), FEs and partial current density of C2+ products (g), formation rate of C2H4 and overall C2+ products (h), half-cell energy efficiency of C2H4 and overall C2+ products (i), long-term stability test of CO2RR at 400 mA cm-2 (j) over m-Cu2O-3 in 1.0 mol L-1 KOH. (k) A comparison of partial current density and FEs of C2H4 over m-Cu2O-3 and the reported Cu-based catalysts (Table S11).

Fig. 3. Characterizations of p-Cu-x and p-Cu-b. TEM (a) and HRTEM (b) images of p-Cu-3. XRD patterns (c), GB densities obtained from HRTEM images (d), the FE of C2H4 and C2+ products as a function of the GB densities (e), normalized Cu K-edge XANES spectra (f), Cu K-edge FT-EXAFS spectra in R space (g), CNs obtained from FT-EXAFS spectra (h), and CNs as a function of the GB densities (i) of p-Cu-x and p-Cu-b.

Fig. 4. Potential-dependent in situ Raman spectra of p-Cu-3 (a-c) and p-Cu-b (e-g) during CO2RR. (d) Deconvolution of *COatop peak to LFB and HFB bands over p-Cu-3. (h,i) Comparison of the *OHad peak intensity in cyclic voltammetry curves of p-Cu-3 and p-Cu-b.

Fig. 5. Potential-dependent in-situ ATR-FTIR spectra of p-Cu-3 (a,b) and p-Cu-b (c,d) during CO2RR. Comparison of the *CO peak area (e) and *COtop/*CObridge ratio (f) as a function of applied potential on p-Cu-3 and p-Cu-b. (g) Schematic illustration of the CO2RR over high GB density p-Cu-3.

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Grain boundary density effect for highly selective C₂₊ production from CO₂ reduction: Polycrystalline Cu electrocatalyst as a paradigm

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