Electrochemical synthesis of Co7Ni3 and Co6Ni4 nanorods with controlled crystalline phase. Application to methanol electro-oxidation

Abstract

CoNi nanorods with modulated crystalline phase have been synthesised by means of a potentiostatic deposition method, using a single electrolytic bath, by only varying the electrodeposition potential. The growth of the nanorods in the interior on the nanochannels of the membrane is mainly controlled by the limited transport of the Co(II) and Ni(II) ions to the growth front. Two types of CoNi nanorods of several microns long, with similar composition but different crystalline phases depending on the applied potential, have been obtained. The potentials for the electrosynthesis of the nanorods have been selected to induce different deposition rates and, as a consequence, different crystalline phases, hcp for the lower deposition rates and fcc (+hcp) for the highest ones. For each selected potential, the nanorods present the same composition and crystalline phase along the rods. The test of the two types of nanorods for the methanol electro-oxidation demonstrated both the specific electrocatalytic behaviour of each one and the promising behaviour of the nanorods as electrocatalysts in direct methanol fuel cells in basic medium, due to their higher surface/volume ratio than that of thin films and the superior stability than that of nanoparticles. The influence of the crystalline phase in the methanol electro-oxidation has been also corroborated from pure-hcp and pure-fcc CoNi films.