It is a great challenge to regulate the precise placement of confined metal species and assemble specific structures at the atomic level. Here we report the design and synthesis of a durable supported-metal-cluster catalyst, Pt@Ge-UTL, that features subnanometric Pt clusters encapsulated inside the extra-large pores of a stabilized UTL-type germanosilicate. Integrated differential phase contrast scanning transmission electron microscopy, in situ X-ray absorption fine structure, 19F magic-angle-spinning NMR, full-range synchrotron pair distribution function G(r) analysis and density functional theory calculations revealed that Pt clusters with an average of four atoms are firmly segregated within 14-membered-ring channels. This is achieved by selectively and directionally anchoring Pt, via Pt–O–Ge bonding, to the UTL zeolite’s unique secondary building units that feature a double-four-membered-ring (d4r) configuration and a Ge-enriched composition. The host–guest bimetallic structure (Pt4-Ge2-d4r@UTL) promotes propane dehydrogenation with high activity, high propylene selectivity and long-term stability. This research demonstrates the use of germanosilicates in the designed synthesis of high-performance propane dehydrogenation catalysts.
Bibliographical noteKAUST Repository Item: Exported on 2023-06-15
Acknowledgements: This work was supported by the National Natural Science Foundation of China (grant numbers 21872052, 21972044, 22172050 and 22105028), the National Key R&D Program of China (2021YFA1501401), ‘Grassland Talents’ of Inner Mongolia Autonomous Region, Young Talents of Science and Technology in Universities of Inner Mongolia Autonomous Region (NJYT23030), ‘Steed plan High level Talents’ of Inner Mongolia University, and Fundamental Research Funds for the Central Universities (grant number 2022CDJXY-003). We gratefully acknowledge the BL17B beamline of the National Facility for Protein Science (NFPS), Shanghai Synchrotron Radiation Facility (SSRF) Shanghai, China for providing the beam time.