Mesoporous PCN‐222‐Supported Mo Single‐Atom Catalysts for Highly Efficient Oxidative Desulfurization

ABSTRACT Oxidative desulfurization (ODS) is a key technology for achieving clean energy production. However, existing molybdenum‐based catalysts commonly suffer from low active sites utilization, limiting their catalytic performance enhancement. In order to significantly improve the activity of Mo‐based catalysts, this study proposes a straightforward one‐step method for preparing Mo single‐atom catalysts using PCN‐222 as the support. Combined with detailed characterization analysis, Mo atoms successfully anchored to ─OH groups adjacent to unsaturated Zr‐oxo nodes and atomically dispersed on the PCN‐222 support, while maintaining the mesoporous structure of PCN‐222. ODS experiments demonstrate that Mo 2 /PCN‐222 completely removes dibenzothiophene (DBT) within 50 min under mild conditions at an extremely low Mo loading (0.23 wt.%), achieving a turnover frequency (TOF) value of 109.36 h −1 , representing a 135‐fold increase over pristine PCN‐222. DFT calculations and other characterizations reveal strong electronic metal‐support interactions between Mo atoms and PCN‐222, significantly promoting rapid electron transfer to the Mo sites, which forms electron‐rich active sites that enhance H 2 O 2 adsorption and activation. This study not only delves into the synergistic interaction between Mo single atoms and PCN‐222 but also offers a novel strategy for designing Mo‐based catalytic systems with high active sites utilization.