MOFs derived acid-base regulation strategies of CuZnAl catalyst for boosting CO2 hydrogenation to methanol

IF 4.9 2区 化学 Q2 CHEMISTRY, PHYSICAL Molecular Catalysis Pub Date : 2025-04-02 DOI:10.1016/j.mcat.2025.115089
Lu Ren , Bin Wang , Yueli Wen , Maohong Fan , Zhaoxiong Huang , Wenxuan Li , Wei Huang , Jing Li , Jianping Guo
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Abstract

Acid-base synergistic effect is crucial in adjusting the catalytic performance of CO2 hydrogenation to methanol, an efficient CO2 emission reduction and carbon recycle strategy. Two MOFs-derived catalysts (CZ-MIL, CA-ZIF) with opposite acid-base properties were tailored by using MIL-68 (Al) and ZIF-8 (Zn) as precursors, and the above two MOFs precursors were hybridized (C-ZAx) to control the acid-base property of the catalyst. C-ZA0.6 (molar ratio of MIL-68 (Al) to ZIF-8 (Zn)=0.6) exhibits a promising catalytic performance with CO2 conversion of 8.9 %, methanol selectivity of 61.85 %, and STY of 117.02 mg mL−1·h−1 at 4 MPa and 523 K. Combined with comprehensive analysis, it is found that methanol selectivity is closely related to weak acid sites arising from the residual skeleton of MIL-68. Acid-base synergy facilitates the hydrogenation of CO2 to methanol. The basic sites are responsible for adsorbing and activating CO2, and the acidic site helps to stabilize CO* and facilitate the further hydrogenation to methanol. This work provides a new idea and feasible method for enhancing the catalytic performance of CO2 hydrogenation to methanol.

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mof衍生CuZnAl催化剂促进CO2加氢制甲醇的酸碱调节策略
酸碱协同效应是调节CO2加氢制甲醇催化性能的关键,是一种高效的CO2减排和碳循环策略。以MIL-68 (Al)和ZIF-8 (Zn)为前驱体,定制了两种酸碱性质相反的MOFs衍生催化剂(CZ-MIL, CA-ZIF),并将这两种MOFs前驱体进行杂化(C-ZAx)以控制催化剂的酸碱性质。MIL-68 (Al)与ZIF-8 (Zn)的摩尔比为0.6时,C-ZA0.6的CO2转化率为8.9%,甲醇选择性为61.85%,在4 MPa和523 K条件下,STY为117.02 mg mL−1·h−1。综合分析发现,MIL-68残留骨架产生的弱酸位点与甲醇选择性密切相关。酸碱协同作用促进CO2加氢生成甲醇。碱性位点负责吸附和活化CO2,酸性位点有助于稳定CO*并促进进一步加氢成甲醇。本研究为提高CO2加氢制甲醇的催化性能提供了新的思路和可行的方法。
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2-methylimidazole
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N,N-dimethylformamide
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p-phthalic acid
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Aluminium chloride hexahydrate
来源期刊
Molecular Catalysis
Molecular Catalysis Chemical Engineering-Process Chemistry and Technology
CiteScore
6.90
自引率
10.90%
发文量
700
审稿时长
40 days
期刊介绍: Molecular Catalysis publishes full papers that are original, rigorous, and scholarly contributions examining the molecular and atomic aspects of catalytic activation and reaction mechanisms. The fields covered are: Heterogeneous catalysis including immobilized molecular catalysts Homogeneous catalysis including organocatalysis, organometallic catalysis and biocatalysis Photo- and electrochemistry Theoretical aspects of catalysis analyzed by computational methods
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