Cu-ZrO2界面精准调控用于CO2加氢制甲醇反应

doi:10.1016/S1872-2067(26)65168-6

催化学报 ›› 2027, Vol. 92: 316-327.DOI: 10.1016/S1872-2067(26)65168-6

Cu-ZrO₂界面精准调控用于CO₂加氢制甲醇反应

赵洁^a,b, 徐广远^a,b, 陈飔^a,b, 严欢^a,b,*

^a中国科学技术大学精准智能化学全国重点实验室, 安徽合肥 230026;
^b中国科学技术大学化学物理系, 安徽合肥 230026

收稿日期:2026-02-11 接受日期:2026-03-16 出版日期:2027-01-18 发布日期:2026-10-30
通讯作者: *电子信箱: yanhuan1@ustc.edu.cn (严欢).
基金资助:
国家重点研发计划(2023YFA1508200); 国家高层次人才青年项目(GG2060007005), 中国科学技术大学重大前沿研究计划(LS2060000002); 中国科学技术大学科研启动经费(KY2060000213, KY2060000204).

Precise tailoring of Cu-ZrO₂ interfaces for CO₂ hydrogenation to methanol

Jie Zhao^a,b, Guangyuan Xu^a,b, Si Chen^a,b, Huan Yan^a,b,*

^aState Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei 230026, Anhui, China;
^bDepartment of Chemical Physics, University of Science and Technology of China, Hefei 230026, Anhui, China

Received:2026-02-11 Accepted:2026-03-16 Online:2027-01-18 Published:2026-10-30
Contact: *E-mail: yanhuan1@ustc.edu.cn (H. Yan).
Supported by:
National Key Research and Development Program of China (2023YFA1508200), the National Natural Science Foundation of China (GG2060007005), the USTC Major Frontier Research Program (LS2060000002), and the USTC Start-up Grant (KY2060000213, KY2060000204).

摘要/Abstract

摘要： 二氧化碳(CO₂)加氢制甲醇被认为是实现碳资源高值转化与可再生能源化学储存的重要途径. Cu-ZrO₂催化体系因在CO₂加氢制甲醇反应中表现出良好的应用前景而备受关注, 其中Cu-ZrO₂界面在CO₂吸附活化、关键中间体转化及催化性能提升中发挥着重要作用. 然而, 传统制备方法对界面结构缺乏有效调控, 难以构筑结构明确、分布均一的Cu-ZrO₂界面, 制约了催化性能的进一步提升, 也阻碍对界面作用机制的深入解析. 因此, 发展界面结构明确且可调的Cu-ZrO₂催化体系, 对揭示界面构效关系并指导高效催化剂设计具有重要意义.
本文以Cu/Al₂O₃为模型催化剂, 采用原子层沉积(ALD)策略在Cu表面可控沉积ZrO₂, 通过调变沉积循环次数构筑了一系列界面结构可调的Cu/Al₂O₃@xZrO₂-A催化剂, 并以传统液相法制备样品作为参照, 比较不同制备策略下催化剂在界面结构、界面性质及反应行为上的差异, 以阐明界面调控对催化性能提升的关键作用. 结构表征结果表明, 相较于传统液相法易形成局部较厚的ZrO₂团聚域, ALD法可在Cu表面构筑分布更均匀、分散度更高的ZrO₂物种, 从而形成均一、结构明确的Cu-ZrO₂界面. 催化评价结果表明, ALD法构筑的Cu-ZrO₂界面更有利于甲醇生成, 其中经过2次ALD循环制备的Cu/Al₂O₃@2ZrO₂-A催化性能最优; 在240 °C和5.0 MPa条件下, 其甲醇时空收率分别达到0.537 g_MeOH g_cat^–1 h^–1和9.59 g_MeOH g_Cu^–1 h^–1. 该催化剂在400 h测试中保持优异耐久性, 与Cu/Al₂O₃催化剂相比稳定性得到明显提升. CO₂-程序升温脱附、电子顺磁共振及X-射线光电子能谱结果表明, Cu/Al₂O₃@2ZrO₂-A中高分散ZrO₂物种赋予催化剂更高浓度的氧空位, 并增强了Cu-ZrO₂界面相互作用. 该界面结构不仅有利于增强CO₂吸附与活化, 而且能有效阻碍Cu颗粒的团聚和烧结. 原位漫反射红外光谱结果表明, 该催化体系中反应主要遵循甲酸盐路径: CO₂首先形成碳酸(氢)盐物种, 随后逐步转化为甲酸盐和甲氧基等中间体, 最终生成甲醇; 其中, 优化后的Cu/Al₂O₃@2ZrO₂-A不仅更有利于碳酸(氢)盐物种的形成, 而且能够促进关键中间体甲酸盐的生成与进一步转化. 综上, ALD方法构筑的均一Cu-ZrO₂界面与富氧空位特征的高分散ZrO₂物种能够协同增强Cu-ZrO₂界面相互作用, 促进CO₂的吸附与活化, 并加快反应中间体的生成与转化, 从而实现催化活性、选择性与稳定性的同步提升, 体现出界面精准调控在催化剂设计中的重要作用.
综上, 本文通过ALD调控ZrO₂在Cu表面的沉积, 可实现Cu-ZrO₂界面结构的有效优化, 从而提升CO₂加氢制甲醇性能. 该工作加深了对Cu-ZrO₂界面构效关系的认识, 并为复杂多相催化体系中界面结构的合理设计提供了新的思路.

关键词: 二氧化碳加氢, 甲醇, 铜–氧化锆界面, 原子层沉积, 氧空位

Abstract: The rational design of metal-oxide interfaces is crucial for efficient CO₂ hydrogenation to methanol. Here, highly dispersed ZrO₂ coating was precisely modulated on the Cu/Al₂O₃ via atomic layer deposition, obtaining a uniform and well-defined Cu-ZrO₂ interfaces. Compared with traditional methods, the optimized Cu/Al₂O₃@2ZrO₂-A catalyst exhibited significantly enhanced CO₂ conversion and methanol selectivity, achieving a methanol space-time yield of 0.537 g_MeOH g-_cat^–1 h^–1 and 9.59 g-_MeOH g_Cu^–1 h^–1 at 240 °C, along with long-term stability over 400 h. Structural and electronic characterizations revealed that uniform Cu-ZrO₂ interfaces with highly dispersed and vacancy-rich ZrO₂ coating were achieved on the Cu/Al₂O₃@2ZrO₂-A catalyst, demonstrating high CO₂ adsorption and activation. In situ spectroscopic studies demonstrated that the uniform and robust Cu-ZrO₂ interface with oxygen vacancy-rich ZrO₂ coating could enhance the formation and transformation of formate intermediate. This work provides a potentially efficient strategy for precisely modulating the interface for other challenging reactions.

Key words: CO₂ hydrogenation, Methanol, Cu-ZrO₂ interface, Atomic layer deposition, Oxygen vacancies

赵洁, 徐广远, 陈飔, 严欢. Cu-ZrO₂界面精准调控用于CO₂加氢制甲醇反应[J]. 催化学报, 2027, 92: 316-327.

Jie Zhao, Guangyuan Xu, Si Chen, Huan Yan. Precise tailoring of Cu-ZrO₂ interfaces for CO₂ hydrogenation to methanol[J]. Chinese Journal of Catalysis, 2027, 92: 316-327.

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Cu-ZrO₂界面精准调控用于CO₂加氢制甲醇反应

Precise tailoring of Cu-ZrO₂ interfaces for CO₂ hydrogenation to methanol

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