Subnanometer Bimetallic Platinum–Zinc Clusters in Zeolites for Propane Dehydrogenation

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 molC3H6 gPt−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/Al2O3 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. A lean, mean, propylene machine: Subnanometer bimetallic Pt–Zn clusters are encapsulated inside silicalite‐1 (S‐1) zeolite via a ligand‐protected direct hydrogen reduction method. In the propane dehydrogenation (PDH) reaction, the PtZn4@S‐1‐H catalyst exhibited a very high propylene selectivity of 99.3 % and specific activity of propylene formation of 65.5 molC3H6 gPt−1 h−1 at 550 °C. Moreover, no obvious deactivation was observed over catalyst even after 13000 min on stream.