Novel 2D-AuSe nanostructures as effective platinum replacement counter electrodes in dye-sensitized solar cells.

Studies to improve the efficiency of dye-sensitized solar cells (DSSCs) include, but are not limited to, finding alternatives such as 2D layered materials as replacement counter electrodes (CEs) to the commonly used Pt. Herein, we report for the first time, the use of AuSe as a counter electrode for the reduction of triiodide ions (I3 -) to iodide ions (I-). The colloidal synthesis of gold selenide nanostructures produced α-AuSe and ß-AuSe dominated products as determined by XRD. Electron microscopy showed α-AuSe having belt-like structures while ß-AuSe had a plate-like morphology. EDS mapping confirmed the elemental composition and homogeneity of the AuSe CEs. Cyclic voltammetry curves of the AuSe CEs displayed the double set of reduction-oxidation peaks associated with the reactions in the I3 -/I- electrolyte and therefore were comparable to the Pt CV curve. The α-AuSe CE showed better electrocatalytic activity with a reduction current of 6.1 mA than that of ß-AuSe and Pt CEs, which were 4.2 mA and 4.8 mA, respectively. The peak-to-peak separation (ΔE pp) for the α-AuSe CE was also more favourable with a value of 532 mV over that of the ß-AuSe CE of 739 mV however, both values were larger than that of the Pt CE, which was found to be 468 mV. The EIS and Tafel plot data showed that α-AuSe had the best catalytic activity compared to ß-AuSe and was comparable to Pt. The DSSC using α-AuSe as a CE had the highest PCE (6.94%) as compared to Pt (4.89%) and ß-AuSe (3.47%). The lower efficiency for Pt was attributed to the poorer fill factor. With these novel results, α-AuSe is an excellent candidate to be used as an alternative CE to Pt in DSSCs.

The effect of the metal and selenium precursors on the properties of NbSe2 and Nb2Se9 nanostructures and their application in dye-sensitized solar cells.

Herein, we report on the effect of the precursors on the structural, morphological, and optical properties of niobium selenide using the heat-up colloidal method. The metal precursor was varied from the conventional NbCl5 to NbF5 whilst Se, SeO2, and selenourea were used as the selenium precursors. The NbCl5 and NbF5 resulted in the formation of NbSe2 and Nb2Se9 respectively. While maintaining the two different metal precursors and varying the selenium precursor from Se, SeO2 to selenourea, the properties of NbSe2 and Nb2Se9 changed slightly, however the effect of changing the selenium precursor was less pronounced than changing the metal precursors. From the XRD and XPS, the NbSe2 nanostructures were more susceptible to oxidation than Nb2Se9 as Nb2O5 was observed in the XRD and the percentage of M-O in the XPS was much higher in NbSe2. NbSe2 formed nanoflowers whilst Nb2Se9 formed rods with 3.29 eV and 2.43 eV band-gaps, respectively. Also, the band-gaps were red-shifted as the selenium precursors were varied. The NbSe2 nanoflowers and Nb2Se9 nanorods were used as counter electrodes in dye-sensitized solar cells. Two methods were used to fabricate the counter electrodes i.e. spin coating and drop casting. The electrochemical properties of the spin coated counter electrodes were better than the drop casted ones; hence, they were employed in dye-sensitized solar cells. The spin coated NbSe2 nanoflowers had the highest efficiency of 6.84%, attributed to the nanoflower morphology.

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.