Single-Atom MnN5 Catalytic Sites Enable Efficient Peroxymonosulfate Activation by Forming Highly Reactive Mn(IV)–Oxo Species
Citations Over TimeTop 1% of 2023 papers
Abstract
Four-nitrogen-coordinated transitional metal (MN4) configurations in single-atom catalysts (SACs) are broadly recognized as the most efficient active sites in peroxymonosulfate (PMS)-based advanced oxidation processes. However, SACs with a coordination number higher than four are rarely explored, which represents a fundamental missed opportunity for coordination chemistry to boost PMS activation and degradation of recalcitrant organic pollutants. We experimentally and theoretically demonstrate here that five-nitrogen-coordinated Mn (MnN5) sites more effectively activate PMS than MnN4 sites, by facilitating the cleavage of the O-O bond into high-valent Mn(IV)-oxo species with nearly 100% selectivity. The high activity of MnN5 was discerned to be due to the formation of higher-spin-state N5Mn(IV)═O species, which enable efficient two-electron transfer from organics to Mn sites through a lower-energy-barrier pathway. Overall, this work demonstrates the importance of high coordination numbers in SACs for efficient PMS activation and informs the design of next-generation environmental catalysts.
Related Papers
- → A first principles study of methanol decomposition on Pd(111): Mechanisms for O–H bond scission and C–O bond scission(2001)86 cited
- → XAS determination of the Fe local environment and oxidation state in phonolite glasses(2011)59 cited
- → Coordination Number of Ternary Mixtures of Spheres†(2003)41 cited
- → The first coordination number for liquid metals(2004)24 cited
- → X-ray absorption spectroscopy investigation of Ba2TiSi2O8+xSiO2 glasses(2001)10 cited