Electrochemistry of undoped diamond nanoparticles: accessing surface redox states

The electrochemical response of an electrode-immobilized layer of undoped, insulating diamond nanoparticles is reported, which we attribute to the oxidation and reduction of surface states. The potentials of these surface states are pH-dependent; moreover they are able to interact with solution redox species. The voltammetric response of redox couples Fe(CN)(6)(3-/4-) and IrCl(6)(3-/2-) are compared at bare boron-doped diamond electrodes and electrodes modified with a layer of nanodiamond (ND). In all cases the presence of ND modifies the CV response at slow scan rates if low concentrations of redox couple are used. Enhancements of oxidation currents are noted at potentials at which the ND surface states can also undergo oxidation, and enhancements of reduction currents are likewise observed where ND is also reducible. We attribute these observations to electron transfer occurring between the species generated at the underlying electrode during CV and the ND immobilized in the interfacial region, leading to regeneration of the starting species and hence enhancement in currents due to a feedback mechanism. The magnitude of current enhancement thus depends on the standard potential of the redox couple relative to those of the ND surface states.