中空花状Cu-Co/ZnFeOx催化二氧化碳加氢合成乙醇

doi:10.15541/jim20260062

摘要/Abstract

摘要： CO₂加氢制乙醇具有实现碳中和与解决能源危机的双重效应, 但其复杂的多步反应机制对催化剂设计提出了严格要求, 传统双金属催化剂存在活性组分易团聚, 致密颗粒结构导致比表面积小及界面调控能力弱等问题。本研究采用溶剂热法制备了中空花状Cu-Co双金属, 与ZnFeO_x机械混合, 开发了Cu-Co/ZnFeO_x复合催化剂。Cu-Co/ZnFeO_x具有分级中空结构、丰富的介孔网络以及较大的比表面积。在H₂: CO₂=3 : 1(体积比)、空速GHSV=12000 mL/(g_cat·h)、300 ℃和1.5 MPa的反应条件下, 与Cu-Co相比, Cu-Co/ZnFeO_x的CO₂转化率由16.9%提高至21.4%, 高碳醇(C₂₊OH)选择性由17.0%提高至26.7%, 乙醇在C₂₊OH中的选择性为61.8%。中空花状的Cu-Co骨架提供了高效的传质通道和丰富的H₂活化位点, ZnFeO_x增强了CO₂吸附与活化能力, Cu-Co和ZnFeO_x之间形成强电子耦合, 协同促进H₂解离和CO₂活化, 其内在电子协同机制表明Cu-Co双金属与ZnFeO_x间存在强金属-载体相互作用, 这种协同效应促进了中间体(CH_x*)的生成与C-C偶联, 有利于关键中间体CH₃CO*和CH₃CH₂O*的形成与稳定, 从而促进乙醇的生成。本研究为设计高效、稳定、低成本的CO₂加氢转化催化剂提供了参考。

关键词: CO₂加氢, 乙醇, Cu-Co, ZnFeO_x

Abstract: CO₂ hydrogenation to ethanol offers the dual benefit of achieving carbon neutrality and addressing energy crises. However, its complex multi-step reaction mechanism imposes stringent requirements on catalyst design. Conventional bimetallic catalysts are limited by issues such as easy agglomeration of active components, low specific surface area due to dense particle structures, and poor interfacial tunability. In this study, hollow flower-like bimetallic Cu-Co was prepared via a solvothermal method, and mechanically mixed with spinel-phase ZnFeO_x to develop a Cu-Co/ZnFeO_x composite catalyst. Cu-Co/ZnFeO_x catalyst features a hierarchical hollow structure with abundant mesoporous networks and a high specific surface area. Under reaction conditions of H₂ : CO₂=3 : 1 (in volume), gas hourly space velocity (GHSV)=12000 mL/(g_cat·h), 300 ℃ and 1.5 MPa, Cu-Co/ZnFeO_x catalyst increases CO₂ conversion from 16.9% to 21.4% compared to Cu-Co alone, raises the selectivity of higher alcohols (C₂₊OH) from 17.0% to 26.7%, and achieves an ethanol selectivity of 61.8% in C₂₊OH. The hollow flower-like Cu-Co framework provides efficient mass transfer pathways and abundant H₂ activation sites, while ZnFeO_x offers high CO₂ adsorption and activation capability. The strong electronic coupling between Cu-Co and ZnFeO_x synergistically promotes the H₂ dissociation and CO₂ activation. The underlying electronic synergy mechanism reveals strong metal-support interactions between the Cu-Co bimetallic and ZnFeO_x. This synergistic effect promotes the formation of intermediates (CH_x*) and C-C coupling, facilitating the formation and stabilization of key intermediates such as CH₃CO* and CH₃CH₂O*, thereby enabling efficient and highly selective ethanol production. This study provides a reference for designing efficient, stable, and low-cost catalysts for CO₂ hydrogenation.

Key words: CO₂ hydrogenation, ethanol, Cu-Co, ZnFeO_x

中图分类号:

TQ426
O643

张强, 卓懋, 查飞, 孟文亮, 田海锋, 唐小华, 郭效军. 中空花状Cu-Co/ZnFeO_x催化二氧化碳加氢合成乙醇[J]. 无机材料学报, DOI: 10.15541/jim20260062.

ZHANG Qiang, ZHUO Mao, ZHA Fei, MENG Wenliang, TIAN Haifeng, TANG Xiaohua, GUO Xiaojun. Catalytic Hydrogenation of Carbon Dioxide to Ethanol by Hollow Flower-like Cu-Co/ZnFeO_x[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20260062.

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