Nanospatial Charge Modulation of Monodispersed Polymeric Microsphere Photocatalysts for Exceptional Hydrogen Peroxide Production

Photocatalysis offers a sustainable strategy for hydrogen peroxide (H2O2) production, which is an essential oxidant and emerging energy carrier in modern chemical industry. The development of polymer‐based photocatalysts to produce H2O2 has great potential but is limited by lower efficiency due to the limitation of light utilization and the low charge separation efficiency. Herein, a series of monodispersed mesoporous resorcinol‐formaldehyde resin spheres (MRFS) are reported with a rational designed spatial charge distribution, exhibiting wide light absorption with a solar‐to‐chemical conversion (SCC) efficiency of 1.1%. Surface photovoltage microscopy (SPVM) measurements unraveled the charge separation in nanospace with uneven distribution of donor (D) and acceptor (A) sites. A density functional theory (DFT) calculation elucidated the origin of photogenerated electrons and holes. Moreover, MRFS demonstrates photocatalytic water oxidation ability. The findings in this work open a new avenue for the development of porous polymeric photocatalysts toward highly efficient solar energy conversion. A series of phenolic resin spheres with different meso‐structures have been developed as state‐of‐art porous polymeric photocatalysts with a solar‐to‐chemical conversion (SCC) efficiency of 1.1% for H2O2 production. These phenolic resin spheres have an uneven distribution of donor (D) and acceptor (A) sites, providing new insights into the nanospatial charge modulation.