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An efficient electrocatalyst for hydrogen evolution has been developed based upon in situ reduction of MoS 2 on ordered mesoporous carbon nanospheres (MoS 2 /MCNs). The properties of MoS 2 /MCNs were characterised by scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. Polarisation curves and electrochemical impedance measurements were obtained for MoS 2 /MCNs modified glassy carbon electrodes. The MoS 2 /MCNs exhibit high catalytic activity for hydrogen evolution with a low overpotential and a very high current density. A theory outlining the origins of the Tafel slope for a Volmer-Heyrovsky (rate determining step) mechanism of hydrogen evolution at MoS 2 catalytic edge sites is presented.

Important aspects of the electrochemical reduction of a series of substituted arene sulfenyl chlorides are investigated. A striking change is observed in the reductive cleavage mechanism as a function of the substituent on the aryl ring of the arene sulfenyl chloride. With p-substituted phenyl chlorides a "sticky" dissociative ET mechanism takes place where a concerted ET mechanism leads to the formation of a radical/anion cluster before decomposition. With o-nitropheyl sulfenyl substituted chlorides a stepwise mechanism is observed where through space S...O interactions play an important role stabilizing both the neutral molecules and their reduced forms. Disulfides are generated through a nucleophilic reaction of the two-electron reduction produced anion (arenethiolate) on the parent molecule. The dissociative electron transfer theory, as well as its extension to the case of strong in-cage interactions between the produced fragments, along with the gas phase chemical quantum calculations results helped rationalize both the observed change in the ET mechanism and the occurrence of the "sticky dissociative" ET mechanism. The radical/anion pair interactions have been determined both in solution as well as in gas phase. This study shows that despite the low magnitude of in-cage interactions in acetonitrile as compared to in the gas phase, their existence strongly affects the kinetics of the involved reactions. It also shows that, as expected, these interactions are reinforced by the existence of strong electron-withdrawing substituents.

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To balance the anchoring sites and conductivity of the catalyst supports is a dilemma in electrocatalytic oxygen reduction reaction (ORR). Nitrogen-doped mesoporous graphene (N-MG) with large surface area, high porosity, and superior intrinsic conductivity has been developed to address this issue. Using N-MG as the backbone, a hybrid catalyst of Co3O4 nanocrystals embedded on N-MG (Co3O4/N-MG) was prepared for the electrocatalytic ORR in alkaline media. The Co3O4/N-MG showed high catalytic activity for the four-electron ORR, giving a more positive onset potential (0.93 V vs RHE) and a higher current density. The unique property of N-MG and the synergetic effect of Co3O4 and N-MG are prominent for ORR. With improved electrocatalytic activity and durability, the Co3O4/N-MG can be an efficient nonprecious metal catalyst and potentially used to substitute the platinum-based cathode catalysts in fuel cells and metal-air batteries.