高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

二氧化碳加氢制甲醇改性二硫化钼催化剂的研究

程耀扬1，林伟志1，乐宇1，李松涛2，李如金2，康金灿1   

  1. 1. 厦门大学化学化工学院，醇醚酯化工清洁生产国家工程实验室 2. 中海石油化学股份有限公司

  • 收稿日期:2025-10-21 修回日期:2025-12-04 网络首发:2025-12-11 发布日期:2025-12-11
  • 通讯作者: 康金灿 E-mail:kangjc@xmu.edu.cn
  • 基金资助:
    国家重点研发计划(2023YFB4103103)和国家自然科学基金(22372136, 22172123)资助

Studies on Modified Molybdenum Disulfide Catalyst for Hydrogenation of Carbon Dioxide to Methanol

Cheng Yaoyang1, Lin Weizhi1 , Le Yu1, Li Songtao2, Li Rujin2, Kang Jincan1   

  1. 1. National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University 2. China BlueChemical Ltd.

  • Received:2025-10-21 Revised:2025-12-04 Online First:2025-12-11 Published:2025-12-11
  • Supported by:
    Supported by the National Key Research and Development Program of China (No. 2023YFB4103103), the National Natural Science Foundation of China (Nos. 22372136 and 22172123)

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摘要： 在“碳达峰、碳中和”背景下，将CO2耦合绿氢转化为甲醇具有重要意义。本文研究了二硫化钼基催化剂，并对其进行改性。首先考察不同钼源、硫源、水热条件对二硫化钼催化剂性能的影响。结果显示，以四水合钼酸铵作钼源、硫脲作硫源、水热温度为190 ℃时催化性能最优，CO2转化率为13.7%，CH3OH选择性为82.0%。对二硫化钼催化剂进行改性研究，发现Zn的引入可提高CO2加氢性能，在1%Zn/MoS2催化剂上催化性能最优，CO2转化率为14.8%，CH3OH选择性为90.5%。该催化剂在150 h内CO2转化率相对稳定，CH3OH选择性随着反应进行逐渐提升并趋于稳定。催化剂表征结果表明，水热法合成的二硫化钼催化剂平均层数为5.5层，层数较少；而Zn的引入既增强了催化剂活化H2能力，提高了CO2转化率，同时又产生了更多硫空位，进而有利于甲醇的选择性生成。本研究为提高CO2转化率、CH3OH选择性和稳定性等催化指标的催化剂设计和开发提供了重要参考。

关键词: CO2加氢, 甲醇合成, 二硫化钼催化剂, Zn改性

Abstract: Amid the global drive for carbon neutrality, the conversion of CO2 into methanol with green hydrogen is of great importance. Herein, we report a comprehensive study on MoS2-based catalysts and their modification for this reaction. First, the effects of different Mo and S precursors as well as hydrothermal conditions on catalytic performance were systematically screened. The optimal catalyst prepared from ammonium tetramolybdate and thiourea at 190 °C delivered a CO2 conversion of 13.7% with an exceptional CH3OH selectivity of 82.0%. Subsequent modification revealed that the introduction of Zn significantly boosts CO2 hydrogenation activity. The 1% Zn/MoS2 catalyst exhibited the best performance, achieving 14.8% CO2 conversion and 90.5% CH3OH selectivity. Over 150 h on-stream, the CO2 conversion remained stable, while CH3OH selectivity gradually increased and then plateaued. Characterization results showed that the hydrothermally synthesized MoS2 possessed an average layer number of ~5.5, indicative of few-layered nanosheets. The incorporation of Zn not only enhanced H2 activation, thereby raising CO2 conversion, but also generated additional sulfur vacancies that beneficial for the methanol formation. These findings provide crucial guidance for the rational design of robust catalysts with simultaneously high activity, selectivity and stability for conversion of CO2 to methanol.

Key words: Carbon dioxide hydrogenation, Methanol synthesis, Molybdenum disulfide catalyst, Modified by Zn

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