The fabrication and electrochemistry of a new class of graphene electrodes are presented. Through high-temperature annealing of hydrazine-reduced graphene oxides followed by high-speed centrifugation and size-selected ultrafiltration, flakes of reduced graphene oxides (r-GOs) of nanometer and submicrometer dimensions, respectively, are obtained and separated from the larger ones. Using n-dodecanethiol-modified Au ultramicroelectrodes of appropriately small sizes, quick dipping in dilute suspensions of these small r-GOs allows attachment of only a single flake on the thiol monolayer. The electrodes thus fabricated are used to study the heterogeneous electron transfer (ET) kinetics at r-GOs and the nanoscopic charge transport dynamics at electrochemical interfaces. The r-GOs are found to exhibit similarly high activity for electrochemical ET reactions to metal electrodes. Voltammetric analysis for the relatively slow ET reaction of Fe(CN)6(3-) reduction produces slightly higher ET rate constants at r-GOs of nanometer sizes than at large ones. These ET kinetic features are in accordance with the defect-dominant nature of the r-GOs and the increased defect density in the nanometer-sized flakes as revealed by Raman spectroscopic measurements. The voltammetric enhancement and inhibition for the reduction of Ru(NH3)6(3+) and Fe(CN)6(3-), respectively, at r-GO flakes of submicrometer and nanometer dimensions upon removal of supporting electrolyte are found to significantly deviate in magnitude from those predicted by the electroneutrality-based electromigration theory, which may evidence the increased penetration of the diffuse double layer into the mass transport layer at nanoscopic electrochemical interfaces.
The large-scale application of acidic water electrolysis as a viable energy storage technology has been hindered by the high demand of precious metal oxides at anode to catalyze the oxygen evolution reaction (OER). We report an Ir–Co binary oxide electrocatalyst for OER fabricated by a multistep process of selective leaching of Co from Co-rich composite oxides prepared through thermal decomposition. The stepwise leaching of the Co component from the composites leads to the formation of macro- and mesoscale voids walled by a cross-linked nanoporous network of rod- and wedge-like building units of Ir–Co binary oxide with a rutile phase structure and an Ir-enriched surface. In comparison, Ir–Co binary oxide with similar composition prepared by direct thermal decomposition method exhibits a loose nanoparticle aggregation morphology with a Co-enriched surface. The cross-linked porous Ir–Co binary oxide from selective leaching is about 3-fold more active for the OER than that from direct thermal decomposition. Compared with pure IrO2 from thermal decomposition, the Co-leached binary oxide is ca. two times more active and is much more durable during continuous oxygen evolution under a constant potential of 1.6 V, thus showing a possibility of reducing the demand of the expensive and scarce Ir in OER electrocatalyst for acidic water splitting.
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