Pt Atomic Site‐Engineered Redox Mediator Boosts Electrosynthesis of Formic Acid from Glycerol

Abstract Electrophilic oxygen‐mediated non‐electrocatalytic processes on Ni‐based catalysts enable highly selective electrosynthesis of formic acid from glycerol. However, this process, usually mediated by dual mediators of Ni 3+ –O and Ni 2+δ –(OH) ads , is significantly plagued by the high potential of Ni 3+ –O. Herein, we report a class of Pt atomic site‐engineered Ni 2+δ –(OH) ads redox mediators without Ni 3+ –O involvement for breaking the dual‐mediator mechanism limitation, achieving efficient formic acid electrosynthesis from glycerol at remarkably low potential. We demonstrate that Pt atomic sites on Ni aerogels can promote Ni 2+δ –(OH) ads generation, thereby circumventing the Ni 3+ –O pathway and favoring initial C─C bond cleavage and sequential hydrogen atom transfer of C 1 intermediates. The resultant Ni 93 Pt 7 exhibits a remarkably low onset potential of only 1.25 V and a high efficiency of 250 C for ∼100% glycerol conversion, outperforming Ni aerogels (1.36 V, 300 C) and catalysts reported previously, along with excellent stability over 180 h. We further demonstrate the broad applicability of this atomic site‐promoted redox mediator engineering for low‐potential electrosynthesis of low‐carbon compounds from other vicinal polyols.