Subnanometric metal species (single atoms and clusters) have been demonstrated to be unique compared with their nanoparticulate counterparts. However, the poor stabilization of subnanometric metal species towards sintering at high temperature (>500 °C) under oxidative or reductive reaction conditions limits their catalytic application. Zeolites can serve as an ideal support to stabilize subnanometric metal catalysts, but it is challenging to localize subnanometric metal species on specific sites and modulate their reactivity. We have achieved a very high preference for localization of highly stable subnanometric Pt and PtSn clusters in the sinusoidal channels of purely siliceous MFI zeolite, as revealed by atomically resolved electron microscopy combining high-angle annular dark-field and integrated differential phase contrast imaging techniques. These catalysts show very high stability, selectivity and activity for the industrially important dehydrogenation of propane to form propylene. This stabilization strategy could be extended to other crystalline porous materials.
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This work has been supported by the European Union through the European Research Council (grant ERC-AdG-2014-671093, SynCatMatch) and the Spanish government through the Severo Ochoa Programme (SEV-2016-0683). L.L. thanks ITQ for providing a contract. The authors also thank the Microscopy Service of UPV for the TEM and STEM measurements. The XAS measurements were carried out in CLAESS beamline at the ALBA synchrotron. HR STEM measurements were performed at DME-UCA in Cadiz University with financial support from FEDER/MINECO (MAT2017-87579-R and MAT2016-81118-P). A relevant patent application (European patent application No. 19382024.8) has been presented. C.W.L. thanks CAPES (Science without Frontiers-Process no. 13191/13-6) for a predoctoral fellowship.
The authors declare no competing interests.
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Liu, L., Lopez-Haro, M., Lopes, C.W. et al. Regioselective generation and reactivity control of subnanometric platinum clusters in zeolites for high-temperature catalysis. Nat. Mater. 18, 866–873 (2019). https://doi.org/10.1038/s41563-019-0412-6
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