晶界密度对CO2还原反应中C2+产物选择性的影响: 以多晶Cu电催化剂为例

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

催化学报 ›› 2026, Vol. 89: 367-377.DOI: 10.1016/S1872-2067(26)65187-X

晶界密度对CO₂还原反应中C₂₊产物选择性的影响: 以多晶Cu电催化剂为例

乔一洙^a^,^b, 金锡雄^a^,^b, 阿博涵^a^,^b, 魏子轩^a^,^b, 王敏^a^,^b, 陈为人^a^,^b, 黄喜^a^,^b, 张玲霞^a^,^b^,^c^,^*(), 施剑林^a^,^b

^a中国科学院上海硅酸盐研究所,关键陶瓷材料全国重点实验室,上海 200050
^b中国科学院大学材料科学与光电技术中心,北京 100049
^c中国科学院大学杭州高等研究院,化学与材料科学学院,浙江杭州 310024

收稿日期:2025-12-24 接受日期:2026-02-16 出版日期:2026-10-18 发布日期:2026-09-01
通讯作者: *电子信箱: zhlingxia@mail.sic.ac.cn (张玲霞).
基金资助:
国家科技重大专项(2026ZD0623702);国家自然科学基金(52672317);上海科学技术委员会(24DZ2201600);上海科学技术委员会(24ZR1475800)

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

Yizhu Qiao^a^,^b, Xixiong Jin^a^,^b, Bohan A^a^,^b, Zixuan Wei^a^,^b, Min Wang^a^,^b, Weiren Chen^a^,^b, Xi Huang^a^,^b, Lingxia Zhang^a^,^b^,^c^,^*(), Jianlin Shi^a^,^b

^aState Key Laboratory of High Performance Ceramics, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
^bCenter of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
^cSchool of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310024, Zhejiang, China

Received:2025-12-24 Accepted:2026-02-16 Online:2026-10-18 Published:2026-09-01
Contact: *E-mail:zhlingxia@mail.sic.ac.cn(L. Zhang).
Supported by:
Advanced Materials-National Science and Technology Major Project(2026ZD0623702);National Natural Science Foundation of China(52672317);Science and Technology Commission of Shanghai(24DZ2201600);Science and Technology Commission of Shanghai(24ZR1475800)

摘要/Abstract

摘要：

化石燃料的广泛使用导致了二氧化碳(CO₂)的过量排放, 从而引发了全球变暖、极端天气等严重的环境危机. 绿电驱动的电催化CO₂还原反应(CO₂RR)能够将CO₂转化为燃料和高附加值化学品, 为封闭碳循环和缓解能源危机提供了一种可行的策略. 在各种CO₂RR产物中, 具有高能量密度和经济价值的多碳化学品(C₂₊)(C₂H₄和n-C₃H₇OH等)是理想的目标产物. 铜(Cu)基电催化剂对关键中间体*CO具有适中的吸附强度, 是目前最具潜力的可将CO₂转化为C₂₊的催化剂. 然而, 复杂的质子耦合电子转移过程、高的碳-碳(C-C)偶联能垒、竞争激烈的析氢反应(HER)和碳一副产物(C₁)导致铜基电催化剂上C₂₊选择性较差. 目前, 引入晶界和界面、在表面构建配位不饱和的铜位点(Cu^δ+, 0 < δ < 1)是提升Cu基催化剂上C₂₊产物选择性的有效策略. 已有研究表明, 通过在金属铜催化剂中构建晶粒间界可提升Cu基催化剂上的C₂₊产物选择性. 然而, 尚未见有效地可控构建和调控晶粒间界的报道, 导致晶粒间界的催化作用机制尚不明确, 成为一个亟待解决的挑战性课题.

本文以初级晶粒粒径可调的介孔氧化亚铜(Cu₂O)作为前驱体, 通过电化学重构合成了一系列具有梯度晶粒间界密度的单组份多晶铜催化剂(p-Cu). 研究发现, 随着晶粒间界密度的提升(37-151 μm^-1), 催化剂中的Cu位点配位数逐渐降低, 同时在流动池CO₂RR中的C₂₊产物选择性也随之提升. 优选的多晶铜催化剂在晶粒间界密度为151 μm^-1、相应的Cu位点配位数为6.36时, C₂₊产物法拉第效率(FE_C2+)和C₂H₄法拉第效率(FE_C2H4)分别达到了88.06%和70.55%, C₂₊产物的分电流密度高达722.7 mA cm^-2. 此外, 该催化剂展现出了良好的稳定性, 在100 h内活性无明显衰减. 原位光谱研究表明, 晶粒间界处的低配位Cu位点在提高催化剂表面*CO覆盖度、提升*CO顶式吸附(*CO_atop)/桥式吸附(*CO_bridge)比例、提供局域强碱性环境等方面发挥了关键作用. 这些效应协同促进了催化剂表面的C-C偶联, 并以能垒更低、动力学更有利的*COH-*CO不对称偶联路径进行, 从而实现了优异的C₂₊产物选择性.

综上, 本研究以初级晶粒粒径可调的介孔Cu₂O纳米晶为前驱体, 通过电化学重构, 成功实现了Cu基催化剂中晶粒间界密度的调控, 并在此基础上建立了晶粒间界密度-Cu位点配位数-C₂₊产物选择性之间的关联, 阐明了Cu基催化剂晶粒间界处低配位Cu位点在CO₂RR中高选择性产C₂₊化学品的作用机制.

关键词: 电催化CO₂还原反应, 介孔纳米晶, 多晶Cu, 晶粒间界, 配位数, 多碳化学品

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

乔一洙, 金锡雄, 阿博涵, 魏子轩, 王敏, 陈为人, 黄喜, 张玲霞, 施剑林. 晶界密度对CO₂还原反应中C₂₊产物选择性的影响: 以多晶Cu电催化剂为例[J]. 催化学报, 2026, 89: 367-377.

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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图/表 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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晶界密度对CO₂还原反应中C₂₊产物选择性的影响: 以多晶Cu电催化剂为例

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

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