Anodic glycerol oxidation to formate facilitating cathodic hydrogen evolution with earth-abundant metal oxide catalysts

•Enhanced electron transport induced by the double-exchange interaction (DEI).•Synergy effect between DEI and nanowhiskers structure facilitates GER.•Co-production of formate and hydrogen delivered 10 mA cm−2 at 1.35 V cell voltage.•In-situ Raman experiments reveal the dynamic evolution of the catalyst surface.•13C isotope-labelling reveal the glycerate regioselective C-C bond cleavage.