Probing the stoichiometry dependent catalytic activity of nickel selenide counter electrodes in the redox reaction of iodide/triiodide electrolyte in dye sensitized solar cells.

Nickel selenide (Ni x Se y ) systems have received much attention in recent years as potential low cost counter electrodes (CEs) in dye sensitized solar cells (DSSCs). Their electrocatalytic activities are comparable to that of the conventional platinum CE. Despite their achievements, the effect of stoichiometry on their catalytic performance as CEs in DSSCs still remains unclear, hence the motivation for this work. Different stoichiometries of Ni x Se y were synthesized via a colloidal method in oleylamine or oleylamine/oleic acid mixture at the appropriate synthetic temperature and Ni to Se precursor ratio. X-ray diffraction revealed that different stoichiometries of nickel selenide were formed namely, NiSe2, Ni3Se4, Ni0.85Se, NiSe and Ni3Se2. Scanning electron microscopy showed that all the stoichiometries had predominantly spherical-like morphologies. Cyclic voltammetry, electrochemical impedance spectroscopy analysis and the photovoltaic performances of the DSSCs fabricated using the different Ni x Se y CEs revealed that selenium rich stoichiometries performed better than the nickel rich ones. Consequently, the catalytic activity towards the redox reaction of the triiodide/iodide electrolyte and hence the power conversion efficiency (PCE) followed the order of NiSe2 > Ni3Se4 > Ni0.85Se > NiSe > Ni3Se2 with PCE values of 3.31%, 3.25%, 3.17%, 2.35% and 1.52% respectively under ambient conditions.

Elucidating the effect of precursor decomposition time on the structural and optical properties of copper(i) nitride nanocubes.

To study the effect of time on the colloidal synthesis of Cu3N nanoparticles, copper(ii) nitrate was thermally decomposed at 260 °C for up to 60 min in octadecylamine as a stabilizing ligand. Thermolysis of the nitrate followed four steps which included; nucleation, growth, ripening and decomposition. At 5 min, partially developed nanocubes were found in a dense population of Cu3N nuclei. Well-defined Cu3N nanocubes were obtained at 15 min with no presence of the nuclei. TEM images showed disintegration of the cubes at 20 min and as time progressed, all the Cu3N decomposed to Cu by 60 min. The formation of the Cu3N nanocubes was confirmed by XRD and XPS. FTIR suggested the formation of a nitrile (RCN) as a result of the thermal decomposition in octadecylamine (ODA) and this was confirmed using NMR and hence, a reaction mechanism was then proposed. The optical properties of the as-synthesized Cu3N were studied using UV-vis and photoluminescence spectroscopies. The absorption spectra for particles synthesized from 5 min to 15 min showed a singular exciton peak while from 20 min to 60 min two peaks were observed. The two peaks may both be associated with the two direct transitions observed in Cu3N or the more red-shifted peak could be a result of localized surface plasmon resonance due to the Cu nanoparticles. Nevertheless, similar to other studies, it is clear that the optical properties of Cu3N are complex.