Ag/Cu耦合催化剂的Cu晶面调控用于电催化二氧化碳还原

doi:10.16085/j.issn.1000-6613.2023-0273

摘要/Abstract

摘要：

电催化二氧化碳还原是降低大气中二氧化碳浓度和缓解温室效应的有效方法。然而，将CO₂电还原为具有高附加值和高能量密度的碳氢化合物或燃料（C₂₊产物）仍然具有十足的挑战性。为了降低大气中二氧化碳浓度和将其转换为有价值的工业品，本文通过优化Ag/Cu耦合催化剂中Cu的晶面，有效地促进了其还原CO₂至C₂H₄和C₂H₅OH等C₂₊产物。利用暴露Cu₂O(100)晶面的Ag/Cu₂O-(100)，暴露Cu₂O(111)晶面的Ag/Cu₂O-(111)以及具有Cu₂O(100)和(111)晶面的Ag/Cu₂O-(100/111)还原制备得到了三种具有不同Cu晶面的Ag/Cu耦合催化剂。控制Cu/Ag比均为30∶1，采用H型电解槽，在CO₂饱和的0.1mol/L KHCO₃电解液中，评估了其CO₂电化学还原性能。其中，具有Cu(100)和Cu(111)晶面的Ag/Cu-(100/111)催化剂展现出最优异的将CO₂还原为C₂₊产物的性能，Cu(100)晶面和(111)晶面的界面有效地促进了C—C耦合，其在-1.3V、-1.5V（vs.RHE）时，C₂₊产物的法拉第效率（FE）均在50%以上，在电位为-1.5V（vs. RHE）时，C₂₊产物的最大FE为57.7%，部分电流密度为8.92mA/cm²。

关键词: Ag/Cu₂O催化剂, 电化学, 二氧化碳, 还原, 形貌, 晶面, C₂₊产物

Abstract:

Electrocatalytic carbon dioxide reduction is an effective method to reduce atmospheric carbon dioxide concentration and mitigate the greenhouse effect. However, electroreduction of CO₂ to hydrocarbons or fuels with high-added value and high energy density(C₂₊ products) remains extremely challenging, which however could be effectively promoted by optimizing the facets of Cu in the Ag/Cu coupled catalysts. Three Ag/Cu coupled catalysts with different Cu facets were obtained by reduction of Ag/Cu₂O-(100) with exposed Cu₂O-(100) facets, Ag/Cu₂O-(111) with exposed Cu₂O-(111) facets, and Ag/Cu₂O-(100/111) with Cu₂O(100) and (111) facets. The CO₂ electrochemical reduction performance was evaluated in an H-type electrolytic cell filled with CO₂-saturated 0.1 M KHCO₃ electrolyte, and the Cu/Ag ratio was controlled as 30∶1. Among them, Ag/Cu-(100/111) catalyst with Cu(100) and Cu(111) facets showed the best performance of reduction CO₂ to C₂₊ productswith aFE of C₂₊ products above 50% at -1.3V and -1.5V vs. RHE. When the potential was -1.5V vs. RHE, the maximum FE of C₂₊ products was 57.7% and the partial current density was 8.92mA/cm².

Key words: Ag/Cu₂O catalyst, electrochemistry, carbon dioxide, reduction, morphology, facets, C₂₊ products

中图分类号:

TQ151.1

刘毅, 房强, 钟达忠, 赵强, 李晋平. Ag/Cu耦合催化剂的Cu晶面调控用于电催化二氧化碳还原[J]. 化工进展, 2023, 42(8): 4136-4142.

LIU Yi, FANG Qiang, ZHONG Dazhong, ZHAO Qiang, LI Jinping. Cu facets regulation of Ag/Cu coupled catalysts for electrocatalytic reduction of carbon dioxide[J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4136-4142.

图/表 10

图1 Ag/Cu2O的结构表征

图2 不同倍数下的SEM图和相应的Cu、Ag EDS谱图

表1 不同形貌催化剂的ICP测试结果

样品	Ag和Cu的占比
Ag/Cu₂O-(100)	1∶29.7
Ag/Cu₂O-(111)	1∶30.1
Ag/Cu₂O-(100/111)	1∶30.4

图3 Ag/Cu催化剂的XRD谱图

图4 Ag/Cu催化剂的SEM图像

图5 Ag/Cu催化剂的透射电镜图像

图6 Ag/Cu-(100/111)的透射元素分析图

图7 Ag/Cu催化剂的产物法拉第效率及C2+产物法拉第效率对比

图8 Ag/Cu催化剂的各种电流密度

图9 Ag/Cu的EIS谱图

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