多孔Cu<sub>2</sub>O立方体电催化还原CO<sub>2</sub>制备乙烯/乙醇

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摘要铜基催化剂能够有效地将二氧化碳电化学还原为多碳C₂₊产物,催化剂的组成和结构是影响C₂₊产物催化活性和选择性的重要因素。本研究旨在考察Cu₂O催化剂多孔结构对电化学还原CO₂的C₂产物选择性的影响。首先通过酸刻蚀实心Cu₂O立方体(S-Cu₂O)制备了具有多孔结构的Cu₂O立方体(P-Cu₂O)。SEM、TEM、XRD、XPS和CV等表征结果表明,S-Cu₂O和P-Cu₂O的组成相同,为混合Cu价态Cu(0)和Cu(I)。2者形貌为约180 nm 立方体,而P-Cu₂O具有不规则的空腔型多孔结构。电化学表征结果表明,P-Cu₂O的电化学活性表面积约为S-Cu₂O的1.75倍,且界面电荷转移电阻比S-Cu₂O低。在N₂和CO₂氛围下的线性伏安扫描 (LSV)结果表明P-Cu₂O具有更高的CO₂催化活性。在气体扩散电极-流动电解池体系进行不同电位下催化剂的电催化还原CO₂反应,考察多孔结构对CO₂还原活性和C₂产物选择性的影响,结果表明,在电位为-1.0 V vs. RHE,电解质为2 mol·L^-1 KOH时,P-Cu₂O的CO₂还原产物选择性达37.7% (C₂H₄: 25.6%, C₂H₅OH: 12.1%),分电流密度达20.9 mA·cm^-2,比S-Cu₂O提高了~28%。以^*COR/[^*COR/CO_(g)]计算关键中间体^*CO深度转化率,结果表明P-Cu₂O的^*CO深度转化明显高于S-Cu₂O。综上,P-Cu₂O对C₂产物选择性的提高归因于:多孔结构使P-Cu₂O具有高活性表面积,提供更多的CO₂还原活性位点,促进CO生成;空腔的结构有利于^*CO局域浓度提高,加速^*CO二聚反应生成C₂产物。为设计和开发电催化还原二氧化碳制多碳产物的Cu₂O基高效催化剂具有重要意义。

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	曹光伟
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关键词：电化学还原二氧化碳铜基催化剂多孔结构 C₂产物

Abstract： Cu₂O catalyst can effectively electrochemically reduce carbon dioxide to multi carbon C₂₊ products. The composition and structure of the catalyst are important factors affecting the catalytic activity and selectivity of C₂₊ products. The purpose of this study was to investigate the effect of porous structure of Cu₂O catalyst on the selectivity of C₂ products for electrochemical reduction of CO₂. Firstly, Cu₂O cubes with porous structure (P-Cu₂O) were prepared by acid etching solid Cu₂O cubes (S-Cu₂O). SEM, TEM, XRD, XPS, CV and other characterization results show that the composition of S-Cu₂O and P-Cu₂O is the same, and they are mixed Cu valence: Cu⁰ and Cu⁺. The morphology of both is about 180 nm cube, while P-Cu₂O has irregular cavity porous structure. The electrochemical characterization results show that the electrochemical active surface area of P-Cu₂O is about 1.75 times that of S-Cu₂O, and the interfacial charge transfer resistance is lower than that of S-Cu₂O. Linear voltammetric scanning (LSV) results in N₂ and CO₂ atmosphere showed that P-Cu₂O had higher CO₂ catalytic activity. The electrocatalytic reduction of CO₂ was carried out under different potentials in the gas diffusion electrode flow cell system. The effects of porous structure on CO₂ reduction activity and C₂ product selectivity were investigated. The results showed that when the potential was -1.0 V vs. RHE and the electrolyte was 2 mol·L^-1 KOH, the CO₂ reduction product selectivity of P-Cu₂O was 37.7% (C₂H₄: 25.6%, C₂H₅OH: 12.1%), and the partial current density was 20.9 mA·cm^-2, which was ~28% higher than that of S-Cu₂O. The deep conversion of key intermediate ^*CO was calculated by ^*COR/[^*COR/CO_(g)]. The results showed that the deep conversion of ^*CO of P-Cu₂O was significantly higher than that of S-Cu₂O. In conclusion, the improvement of the selectivity of P-Cu₂O for C₂ products is attributed to: the porous structure makes P-Cu₂O have high active surface area, provides more CO₂ reduction active sites and promotes the formation of CO; the structure of the cavity is conducive to increase the local concentration of ^*CO and accelerate the dimerization of ^*CO to produce C₂ product. This study is of great significance for the design and development of Cu₂O based high-efficiency catalysts for electrocatalytic reduction of carbon dioxide to multi carbon products.

Keywords： electroreduction CO₂ Cu-based catalysts porous structure C₂ products

Received 2022-05-01;

Fund:国家自然科学基金(22178266)。

Corresponding Authors: 王华,副教授,E-mail:tjuwanghua@tju.edu.cn。 Email: tjuwanghua@tju.edu.cn

About author: 曹光伟(1997-),男,硕士研究生,现从事电催化还原CO₂方面的研究。

引用本文:

曹光伟, 曹雪蕊, 王华.多孔Cu₂O立方体电催化还原CO₂制备乙烯/乙醇[J]. 化学工业与工程, 2023,40(6): 15-27

CAO Guangwei, CAO Xuerui, WANG Hua.Preparation of ethylene/ethanol by electrocatalytic reduction of CO₂ with porous Cu₂O cube[J]. Chemcial Industry and Engineering, 2023,40(6): 15-27

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