Polyoxometalates‐Mediated Selectivity in Pt Single‐Atoms on Ceria for Environmental Catalysis

Abstract Optimizing the reactivity and selectivity of single‐atom catalysts (SACs) remains a crucial yet challenging issue in heterogeneous catalysis. This study demonstrates selective catalysis facilitated by a polyoxometalates‐mediated electronic interaction (PMEI) in a Pt single‐atom catalyst supported on CeO 2 modified with Keggin‐type phosphotungstate acid (HPW), labeled as Pt 1 /CeO 2 ‐HPW. The PMEI effect originates from the unique arrangement of isolated Pt atoms and HPW clusters on the CeO 2 support. Electrons are transferred from the ceria support to the electrophilic tungsten in HPW clusters, and subsequently, Pt atoms donate electrons to the now electron‐deficient ceria. This phenomenon enhances the positive charge of Pt atoms, moderating O 2 activation and limiting lattice oxygen mobility compared to the conventional Pt 1 /CeO 2 catalyst. The resulting electronic structure of Pt combined with the strong and local acidic environment of HPW on Pt 1 /CeO 2 ‐HPW leads to improved efficiency and N 2 selectivity in the degradation of NH 3 and NO, as well as increased CO 2 yield when inputting volatile organic compounds. This study sheds the light on the design of SACs with balanced reactivity and selectivity for environmental catalysis.