Tailoring the Morphology of Mesoporous Titania Thin Films through Biotemplating with Nanocrystalline Cellulose

The tunable porosity of titania thin films is a key factor for successful applications in photovoltaics, sensing, and photocatalysis. Here, we report on nanocrystalline cellulose (NCC) as a novel shape-persistent templating agent enabling the straightforward synthesis of mesoporous titania thin films. The obtained structures are highly porous anatase morphologies having well-defined, narrow pore size distributions. By varying the titania-to-template ratio, it is possible to tune the surface area, pore size, pore anisotropy, and dimensions of titania crystallites in the films. Moreover, a post-treatment at high humidity and subsequent slow template removal can be used to achieve pore widening; this treatment is also beneficial for the multilayer deposition of thick films. The resulting homogeneous transparent films can be directly spin- or dip- coated on glass, silicon, and transparent conducting oxide (TCO) substrates. The mesoporous titania films show very high activity in the photocatalytic NO conversion and in the degradation of 4-chlorophenol. Furthermore, the films can be successfully applied as anodes in dye-sensitized solar cells

Nanocellulose-Assisted Formation of Porous Hematite Nanostructures

We report the formation of porous iron oxide (hematite) nanostructures via sol–gel transformations of molecular precursors in the confined space of self-organized nanocrystalline cellulose (NCC) used as a shape-persistent template. The obtained structures are highly porous α-Fe₂O₃ (hematite) morphologies with a well-defined anisotropic porosity. The character of the porous nanostructure depends on the iron salt used as the precursor and the heat treatment. Moreover, a postsynthetic hydrothermal treatment of the NCC/iron salt composites strongly affects the crystal growth as well as the porous nanomorphology of the obtained hematite scaffolds. We demonstrate that the hydrothermal treatment alters the crystallization mechanism of the molecular iron precursors, which proceeds via the formation of anisotropic iron oxyhydroxide species. The nanocellulose templating technique established here enables the straightforward fabrication of a variety of mesoporous crystalline iron oxide scaffolds with defined porous structure and is particularly attractive for the processing of porous hematite films on different substrates

Nanocellulose-Templated Porous Titania Scaffolds Incorporating Presynthesized Titania Nanocrystals

Nanocrystalline cellulose (NCC) is an abundant biogenic nanomaterial with unique properties that enables the efficient synthesis of mesoporous crystalline titania. We significantly enhance the photocatalytic activity of titania thin films by introducing solvothermally synthesized preformed anatase nanoparticles into a sol–gel based biotemplated titania scaffold. The resulting dual source titania thin films containing different amounts of preformed crystalline species were investigated by time-resolved microwave conductivity (TRMC) measurements and tested in the photocatalytic conversion of 4-chlorophenol. The gradual addition of preformed nanoparticles leads to a consistent increase of the mean size of titania crystalline domains, whereas the porosity of the composite is well-preserved due to the shape-persistent nature of the NCC template. Microwave conductivity studies establish increased photoconductivity of the films containing preformed anatase nanoparticles in comparison to that of films made without the nanoparticles. The synergistic features of the dual source titania, namely the improved crystalline properties brought by the preformed nanocrystals in combination with the high surface area provided by the NCC-templated sol–gel titania, result in a very high photocatalytic activity of the films in the photocatalytic decomposition of 4-chlorophenol. In quantitative terms, the dual source titania films prepared with 75% nanoparticles exhibit a first order degradation rate constant of 0.53 h^–1 (1.47 × 10⁻⁴ sec⁻¹), which strongly outperforms the activity of commercial P90 nanopowder showing a rate constant of 0.17 h^–1 (0.47 × 10⁻⁴ sec⁻¹) under the same conditions

Nanostructured Ternary FeCrAl Oxide Photocathodes for Water Photoelectrolysis

A sol–gel method for the synthesis of semiconducting FeCrAl oxide photocathodes for solar-driven hydrogen production was developed and applied for the production of meso- and macroporous layers with the overall stoichiometry Fe_0.84Cr_1.0Al_0.16O₃. Using transmission electron microscopy and energy-dispersive X-ray spectroscopy, phase separation into Fe- and Cr-rich phases was observed for both morphologies. Compared to prior work and to the mesoporous layer, the macroporous FeCrAl oxide photocathode had a significantly enhanced photoelectrolysis performance, even at a very early onset potential of 1.1 V vs RHE. By optimizing the macroporous electrodes, the device reached current densities of up to 0.68 mA cm^–2 at 0.5 V vs RHE under AM 1.5 with an incident photon-to-current efficiency (IPCE) of 28% at 400 nm without the use of catalysts. Based on transient measurements, this performance increase could be attributed to an improved collection efficiency. At a potential of 0.75 V vs RHE, an electron transfer efficiency of 48.5% was determined

Passivation of PbS Quantum Dot Surface with l‑Glutathione in Solid-State Quantum-Dot-Sensitized Solar Cells

Surface oxidation of quantum dots (QDs) is one of the biggest challenges in quantum dot-sensitized solar cells (QDSCs), because it introduces surface states that enhance electron–hole recombination and degrade device performance. Protection of QDs from surface oxidation by passivating the surface with organic or inorganic layers can be one way to overcome this issue. In this study, solid-state QDSCs with a PbS QD absorber layer were prepared from thin mesoporous TiO₂ layers by the successive ionic layer adsorption/reaction (SILAR) method. Spiro-OMeTAD was used as the organic p-type hole transporting material (HTM). The effects on the solar cell performance of passivating the surface of the PbS QDs with the tripeptide l-glutathione (GSH) were investigated. Current–voltage characteristics and external quantum efficiency measurements of the solar cell devices showed that GSH-treatment of the QD-sensitized TiO₂ electrodes more than doubled the short circuit current and conversion efficiency. Impedance spectroscopy, intensity-modulated photovoltage and photocurrent spectroscopy analysis of the devices revealed that the enhancement in solar cell performance of the GSH-treated cells originates from improved charge injection from PbS QDs into the conduction band of TiO₂. Time-resolved photoluminescence decay measurements show that passivation of the surface of QDs with GSH ligands increases the exciton lifetime in the QDs