Visualizing Element Migration over Bifunctional Metal‐Zeolite Catalysts and its Impact on Catalysis

• Published in: Angewandte Chemie International Edition Vol. 60; no. 32; pp. 17735 - 17743
• Main Authors: Wang, Yuhao, Wang, Genyuan, Wal, Lars I., Cheng, Kang, Zhang, Qinghong, Jong, Krijn P., Wang, Ye
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 02.08.2021
• Edition: International ed. in English
• Subjects: Acidity; bifunctional catalysis; Carbon dioxide; Catalysis; catalyst deactivation; Catalysts; Chromium; Chromium oxides; CO2 utilization; Electron microscopy; Heavy metals; heterogeneous catalysis; Hydrocarbons; Indium oxides; Physicochemical properties; Selectivity; Thermomigration; Zeolites; Zinc oxide; Zirconium; Zirconium dioxide
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202107264

The catalytic performance of composite catalysts is not only affected by the physicochemical properties of each component, but also the proximity and interaction between them. Herein, we employ four representative oxides (In2O3, ZnO, Cr2O3, and ZrO2) to combine with H‐ZSM‐5 for the hydrogenation of CO2 to hydrocarbons directed by methanol intermediate and clarify the correlation between metal migration and the catalytic performance. The migration of metals to zeolite driven by the harsh reaction conditions can be visualized by electron microscopy, meanwhile, the change of zeolite acidity is also carefully characterized. The protonic sites of H‐ZSM‐5 are neutralized by mobile indium and zinc species via a solid ion‐exchange mechanism, resulting in a drastic decrease of C2+ hydrocarbon products over In2O3/H‐ZSM‐5 and ZnO/H‐ZSM‐5. While, the thermomigration ability of chromium and zirconium species is not significant, endowing Cr2O3/H‐ZSM‐5 and ZrO2/H‐ZSM‐5 catalysts with high selectivity of C2+ hydrocarbons. The catalytic behaviors of bifunctional oxide‐zeolite catalysts for the hydrogenation of CO2 were significantly influenced by element migration, which was dependent on the type of oxides and affected synergy of the two functional components.