Developing an efficient
material as a counter electrode (CE) with
excellent catalytic activity, intrinsic stability, and low cost is
essential for the commercial application of dye-sensitized solar cells
(DSSCs). Transition metal phosphides have been demonstrated as outstanding
multifunctional catalysts in a broad range of energy conversion technologies.
Here, we exploited different phases of iron phosphide as CEs in DSSCs
with an I–/I3
–-based
electrolyte. Solvothermal synthesis using a triphenylphosphine precursor
as a phosphorus source allows to grow a Fe2P phase at 300
°C and a FeP phase at 350 °C. The obtained iron phosphide
catalysts were coated on fluorine-doped tin oxide substrates and heat-treated
at 450 °C under an inert gas atmosphere. The solar-to-current
conversion efficiency of the solar cells assembled with the Fe2P material reached 3.96 ± 0.06%, which is comparable
to the device assembled with a platinum (Pt) CE. DFT calculations
support the experimental observations and explain the fundamental
origin behind the improved performance of Fe2P compared
to FeP. These results indicate that the Fe2P catalyst exhibits
excellent performance along with desired stability to be deployed
as an efficient Pt-free alternative in DSSCs.
The functionalization of photocatalytic metal oxide nanoparticles of TiO 2 , ZnO, WO 3 and CuO with amineterminated (oleylamine) and thiol-terminated (dodecane-1thiol) alkyl-chain ligands was studied under ambient conditions. A high selectivity was observed in the binding specificity of a ligand towards nanoparticles of these different oxides. It was observed that oleylamine binds stably to only TiO 2 and WO 3 , whereas dodecane-1-thiol binds stably only to ZnO and CuO. Similarly, polar-to-nonpolar solvent phase transfer of TiO 2 and WO 3 nanoparticles could be achieved by using oleylamine, but not dodecane-1-thiol, whereas the opposite holds for ZnO and CuO. The surface chemistry of ligand-functionalized nanoparticles was probed by attenu-ated total reflectance (ATR)-FTIR spectroscopy, which enabled the occupation of the ligands at the active sites to be elucidated. The photostability of the ligands on the nanoparticle surface was determined by the photocatalytic selfcleaning properties of the material. Although TiO 2 and WO 3 degrade the ligands within 24 h under both UV and visible light, ligands on ZnO and CuO remain unaffected. The gathered insights are also highly relevant from an application point of view. As an example, because the ligand-functionalized nanoparticles are hydrophobic in nature, they can be self-assembled at the air-water interface to give nanoparticle films with demonstrated photocatalytic as well as antifogging properties.
While the behaviour of plasmonic solid thin films in the Kretschmann (also known as Attenuated Total Reflection, ATR) configuration is well-understood, the use of discrete nanoparticle arrays in this optical configuration is not thoroughly explored. It is important to do so, since close packed plasmonic nanoparticle arrays exhibit exceptionally strong light-matter interactions by plasmonic coupling. The present work elucidates the optical properties of plasmonic Au and Ag nanoparticle arrays in both the direct normal incidence and Kretschmann configuration by numerical models, that are validated experimentally. First, hexagonal close packed Au and Ag nanoparticle films/arrays are obtained by air–liquid interfacial assembly. The numerical models for the rigorous solution of the Maxwell’s equations are validated using experimental optical spectra of these films before systematically investigating various parameters. The individual far-field/near-field optical properties, as well as the plasmon relaxation mechanism of the nanoparticles, vary strongly as the packing density of the array increases. In the Kretschmann configuration, the evanescent fields arising from p- and s-polarized (or TM and TE polarized) incidence have different directional components. The local evanescent field intensity and direction depends on the polarization, angle of incidence and the wavelength of incidence. These factors in the Kretschmann configuration give rise to interesting far-field as well as near-field optical properties. Overall, it is shown that plasmonic nanoparticle arrays in the Kretschmann configuration facilitate strong broadband absorptance without transmission losses, and strong near-field enhancement. The results reported herein elucidate the optical properties of self-assembled nanoparticle films, pinpointing the ideal conditions under which the normal and the Kretschmann configuration can be exploited in multiple light-driven applications.
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