Subnanometer Bimetallic Platinum-Zinc Clusters in Zeolites for Propane Dehydrogenation

Qiming Sun; Ning Wang; Qiyuan Fan; Lei Zeng; Alvaro Mayoral; Shu Miao; Ruoou Yang; Zheng Jiang; Wei Zhou; Jichao Zhang; Tianjun Zhang; Jun Xu; Peng Zhang; Jun Cheng; Dong-Chun Yang; Ran Jia; Lin Li; Qinghong Zhang; Ye Wang; Osamu Terasaki; Jihong Yu

doi:10.1002/anie.202003349

Subnanometer Bimetallic Platinum-Zinc Clusters in Zeolites for Propane Dehydrogenation

Angew Chem Int Ed Engl. 2020 Oct 26;59(44):19450-19459. doi: 10.1002/anie.202003349. Epub 2020 May 11.

Authors

Qiming Sun¹, Ning Wang¹, Qiyuan Fan², Lei Zeng², Alvaro Mayoral³, Shu Miao⁴, Ruoou Yang⁵, Zheng Jiang^{5

6}, Wei Zhou², Jichao Zhang⁵, Tianjun Zhang¹, Jun Xu⁷, Peng Zhang⁸, Jun Cheng², Dong-Chun Yang⁹, Ran Jia⁹, Lin Li¹⁰, Qinghong Zhang², Ye Wang², Osamu Terasaki³, Jihong Yu^{1

11}

Affiliations

¹ State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012, P. R. China.
² 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.
³ Center for High-resolution Electron Microscopy (CħEM), School of Physical Science and Technology, ShanghaiTech University, Shanghai, 201210, P. R. China.
⁴ JEOL (Beijing) Co., Ltd., Beijing, 100080, P. R. China.
⁵ Shanghai Synchrotron Radiation Facility, Zhangjiang National Lab, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201204, P. R. China.
⁶ Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201800, P. R. China.
⁷ Wuhan Center for Magnetic Resonance, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan, 430071, P. R. China.
⁸ Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, B3H 4R2, Canada.
⁹ Institute of Theoretical Chemistry, Jilin University, Changchun, 130023, P. R. China.
¹⁰ Electron Microscopy Center, Jilin University, Changchun, 130012, P. R. China.
¹¹ International Center of Future Science, Jilin University, Qianjin Street 2699, Changchun, 130012, P. R. China.

PMID: 32259339
DOI: 10.1002/anie.202003349

Abstract

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^-1 and specific activity of propylene formation of 65.5 mol $_{C_{3} H_{6}}$ g_Pt ^-1 h^-1 (WHSV=108 h^-1 ) 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^-1 ), affording an extremely low deactivation constant of 0.001 h^-1 , which is 200 times lower than that of the PtZn4/Al₂ O₃ 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.

Keywords: Pt-Zn clusters; confinement synthesis; heterogeneous catalysis; propane dehydrogenation; zeolites.

Abstract

Grants and funding