Selective electrochemical methanol to formate conversion via direct CHO hydroxylation on Ptδ+-Ptδ– dipoles

The electrochemical upgrading of methanol to formate is constrained by CO poisoning from *CHO intermediate dehydrogenation, hindering its industrial application. Herein, we report that engineering atomically polarized Pt δ+ -Pt δ– dipoles on Ti felt achieves a formate Faradaic efficiency of 99% at +0.9 V vs . RHE, which is better than that of commercial Pt/C (62%). Moreover, a formate production rate of 945 mmol g Pt –1 h –1 is achieved with stable performance for more than 5 days at 100 mA cm –2 . These dipoles comprise spatially adjacent electron-deficient Pt δ+ bonded to lattice O and electron-rich Pt δ– coordinated to unsaturated Ti atoms working synergistically. The Pt δ+ site dehydrogenates CH 3 OH to *CHO, which adsorbs across the dipole in a side-on Pt δ+ –OHC–Pt δ– bridging configuration. Within this configuration, Pt δ– donates electrons via d → π * backdonation to the π * antibonding orbital of *CHO, steering its direct hydroxylation and generating electrostatic repulsion for rapid HCOOH desorption. This strategy reduces environmental impact by 88% and carbon emissions by 11% relative to conventional thermal routes, demonstrating the potential of dipole engineering for C 1 electrochemistry.