In-situ Raman unveiled Nb-O-bond-dependency selectivity for methanol electro-oxidation at high current density

Selective methanol oxidation reaction (MOR) to value-added formate can maximize the energy utilization by replacing the high onset-potential and sluggish oxygen evolution reaction. However, to date, only first-row 3d transition metal oxides exhibit the capacity of selective MOR, motivating the design of new kinds of electrocatalysts to further enhance the performance. Here we develop amorphous Nb2O5 as an efficient electrocatalyst, for the first time, for selective MOR to formate, with a low operating potential of 1.47 V vs. RHE to achieve the industry-relevant current densities (>100 mA cm-2) with a formate Faradaic efficiency of ~100%. We demonstrate, via operando Raman measurements, that this superior electrochemical MOR capacity originates from the in-situ induced short Nb-O bonds from the amorphous structure. Besides, the interface between amorphous Nb2O5 and nickel foam could also faciltate the MOR. This work may provide insights for designing novel transition metal oxides as efficient catalysts for selective MOR.