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 PO 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.