Effect of the Synthetic Method on the Properties of Ni-Based Hydrogen Oxidation Catalysts.

The latest progress in alkaline anion-exchange membranes has led to the expectation that less costly catalysts than those of the platinum-group metals may be used in anion-exchange membrane fuel cell devices. In this work, we compare structural properties and the catalytic activity for the hydrogen-oxidation reaction (HOR) for carbon-supported nanoparticles of Ni, Ni3Co, Ni3Cu, and Ni3Fe, synthesized by chemical and solvothermal reduction of metal precursors. The catalysts are well dispersed on the carbon support, with particle diameter in the order of 10 nm, and covered by a layer of oxides and hydroxides. The activity for the HOR was assessed by voltammetry in hydrogen-saturated aqueous solutions of 0.1 mol dm-1 KOH. A substantial activation by potential cycling of the pristine catalysts synthesized by solvothermal reduction is necessary before these become active for the HOR; in situ Raman spectroscopy shows that after activation the surface of the Ni/C, Ni3Fe, and Ni3Co catalysts is fully reduced at 0 V, whereas the surface of the Ni3Cu catalyst is not. The activation procedure had a smaller but negative impact on the catalysts synthesized by chemical reduction. After activation, the exchange-current densities normalized with respect to the ECSA (electrochemically active surface area) were approximately independent of composition but relatively high compared to catalysts of larger particle diameter.