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 Ptδ+-Ptδ- 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 gPt-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 Ptδ+ bonded to lattice O and electron-rich Ptδ- coordinated to unsaturated Ti atoms working synergistically. The Ptδ+ site dehydrogenates CH3OH to *CHO, which adsorbs across the dipole in a side-on Ptδ+-OHC-Ptδ- bridging configuration. Within this configuration, Ptδ- 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 C1 electrochemistry.