https://doi.org/10.1021/acs.est.3c06878

Surface-Phosphorylated Ceria for Chlorine-Tolerance Catalysis | Environmental Science & Technology (acs.org)

An improved fundamental understanding of active site structures can unlock opportunities for catalysis from conceptual design to industrial practice. Herein, we present the computational discovery and experimental demonstration of a highly active surface-phosphorylated ceria catalyst that exhibits robust chlorine tolerance for catalysis. Ab initio molecular dynamics (AIMD) calculations and in situ near-ambient pressure X-ray photoelectron spectroscopy (in situ NAP-XPS) identified a predominantly HPO4 active structure on CeO2(110) and CeO2(111) facets at room temperature. Importantly, further elevating the temperature led to a unique hydrogen (H) atom hopping between coordinatively unsaturated oxygen and the adjacent P═O group of HPO4. Such a mobile H on the catalyst surface can effectively quench the chlorine radicals (Cl•) via an orientated reaction analogous to hydrogen atom transfer (HAT), enabling the surface-phosphorylated CeO2-supported monolithic catalyst to exhibit both expected activity and stability for over 68 days during a pilot test, catalyzing the destruction of a complex chlorinated volatile organic compound industrial off-gas.

有幸参与，很早之前发现H Hopping在氧化铈用于CVOCs催化燃烧时可能有所作用，翁教授做了全面的考察！