Highly Selective Photocatalytic Synthesis of Acetic Acid at 0–25 °C

Abstract Acetic acid (AA), a vital compound in chemical production and materials manufacturing, is conventionally synthesized by starting with coal or methane through multiple steps including high‐temperature transformations. Here we present a new synthesis of AA from ethane through photocatalytic selective oxidation of ethane by H 2 O 2 at 0–25 °C. The catalyst designed for this process comprises g‐C 3 N 4 with anchored Pd 1 single‐atom sites. In situ studies and computational simulation suggest the immobilized Pd 1 atom becomes positively charged under photocatalytic condition. Under photoirradiation, the holes on the Pd 1 single‐atom of OH−Pd 1 /g‐C 3 N 4 serves as a catalytic site for activating a C−H instead of C−C of C 2 H 6 with a low activation barrier of 0.14 eV, through a concerted mechanism. Remarkably, the selectivity for synthesizing AA reaches 98.7 %, achieved under atmospheric pressure of ethane at 0 °C. By integrating photocatalysis with thermal catalysis, we introduce a highly selective, environmentally friendly, energy‐efficient synthetic route for AA, starting from ethane, presenting a promising alternative for AA synthesis. This integration of photocatalysis in low‐temperature oxidation demonstrates a new route of selective oxidation of light alkanes.