Hydrogen Evolution in Neutral Media by Differential Intermediate Binding at Charge-Modulated Sites of a Bimetallic Alloy Electrocatalyst

The energy barrier to dissociate neutral water has been lowered by the differential intermediate binding on the charge-modulated metal centers of Co85Mo15 sheets supported on Ni-foam (NF), where the overpotential for hydrogen evolution reaction (HER) in 1 M phosphate buffer solution (PBS) is only 50 +/- 9 mV at -10 mA cm-2. It has a turnover frequency (TOF) of 0.18 s-1, mass activity of 13.2 A g-1 at -200 mV vs. reversible hydrogen electrode (RHE), and produces 16 ml H2 h-1 at -300 mV vs. RHE, more than double that of 20 % Pt/C. The Mo delta+ and Co delta- sites adsorb OH*, and H*, respectively, and the electron injection from Co to H-O-H cleaves the O-H bond to form the Mo-OH* intermediate. Operando spectral analyses indicate a weak H-bonded network for facilitating the H2O*/OH* transport, and a potential-induced reversal of the charge density from Co to the more electronegative Mo, because of the electron withdrawing Co-H* and Mo-OH* species. Co85Mo15/NF can also drive the complete electrolysis of neutral water at only 1.73 V (10 mA cm-2). In alkaline, and acidic media, it demonstrates a Pt-like HER activity, accomplishing -1000 mA cm-2 at overpotentials of 161 +/- 7, and 175 +/- 22 mV, respectively. The energy barrier to dissociate neutral water has been lowered by the differential binding of H* and OH* on the charge-modulated metal centers of amorphous Co85Mo15 sheets supported on Ni-foam, resulting in an ultralow overpotential of 50 +/- 9 mV vs. the reversible hydrogen electrode at a current density of -10 mA cm-2. image