用于丙烷脱氢的沸石中的亚纳米双金属铂 - 锌簇
Subnanometer Bimetallic Platinum-Zinc Clusters in Zeolites for Propane Dehydrogenation.
作者信息
Sun Qiming, Wang Ning, Fan Qiyuan, Zeng Lei, Mayoral Alvaro, Miao Shu, Yang Ruoou, Jiang Zheng, Zhou Wei, Zhang Jichao, Zhang Tianjun, Xu Jun, Zhang Peng, Cheng Jun, Yang Dong-Chun, Jia Ran, Li Lin, Zhang Qinghong, Wang Ye, Terasaki Osamu, Yu Jihong
机构信息
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012, P. R. China.
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, National Engineering Laboratory for Green Chemical, Productions of Alcohols, Ethers and Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. China.
出版信息
Angew Chem Int Ed Engl. 2020 Oct 26;59(44):19450-19459. doi: 10.1002/anie.202003349. Epub 2020 May 11.
Propane dehydrogenation (PDH) has great potential to meet the increasing global demand for propylene, but the widely used Pt-based catalysts usually suffer from short-term stability and unsatisfactory propylene selectivity. Herein, we develop a ligand-protected direct hydrogen reduction method for encapsulating subnanometer bimetallic Pt-Zn clusters inside silicalite-1 (S-1) zeolite. The introduction of Zn species significantly improved the stability of the Pt clusters and gave a superhigh propylene selectivity of 99.3 % with a weight hourly space velocity (WHSV) of 3.6-54 h and specific activity of propylene formation of 65.5 mol g h (WHSV=108 h ) at 550 °C. Moreover, no obvious deactivation was observed over PtZn4@S-1-H catalyst even after 13000 min on stream (WHSV=3.6 h ), affording an extremely low deactivation constant of 0.001 h , which is 200 times lower than that of the PtZn4/Al O counterpart under the same conditions. We also show that the introduction of Cs ions into the zeolite can improve the regeneration stability of catalysts, and the catalytic activity kept unchanged after four continuous cycles.
丙烷脱氢（PDH）在满足全球对丙烯日益增长的需求方面具有巨大潜力，但广泛使用的铂基催化剂通常存在短期稳定性差和丙烯选择性不理想的问题。在此，我们开发了一种配体保护的直接氢还原方法，用于将亚纳米双金属Pt-Zn团簇封装在硅沸石-1（S-1）分子筛内。锌物种的引入显著提高了铂团簇的稳定性，并在550℃下实现了99.3%的超高丙烯选择性，重量时空速（WHSV）为3.6 - 54 h⁻¹，丙烯生成的比活性为65.5 mol g⁻¹ h⁻¹（WHSV = 108 h⁻¹）。此外，即使在13000分钟的连续运行后（WHSV = 3.6 h⁻¹），PtZn₄@S-1-H催化剂也未观察到明显失活，失活常数极低，为0.001 h⁻¹，这比相同条件下的PtZn₄/Al₂O₃催化剂低200倍。我们还表明，将铯离子引入分子筛可以提高催化剂的再生稳定性，并且在四个连续循环后催化活性保持不变。
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