Controlled Synthesis of Chromium-Oxide-Based Protective Layers on Pt:Influence of Layer Thickness on Selectivity

Chromium-oxyhydroxide (CrxOyHz)-based thin films have previously been shown in photocatalysis and industrial chlorate production to prevent unwanted reduction reactions to occur, thereby enhancing the selectivity for hydrogen evolution and thus the overall process efficiency. Here, a highly reproducible synthesis protocol was developed to allow for the electrodeposition of CrxOyHz-based thin films with controlled thickness in the range of the sub-monolayer up to (>4) multilayer coverage. Electrodeposited CrxOyHz coatings were electrochemically characterized using voltammetry and stripping experiments, allowing thickness-dependent film selectivity to be deduced in detail. The results are discussed in terms of mass transport properties and structure of the electrodeposited chromium oxyhydroxide films. It is shown that the permeation of diatomic probe molecules, such as O2 and CO, was significantly reduced by films as thin as four monolayers. Importantly, it is shown that the prepared thin film coatings enabled prolonged hydrogen oxidation in the presence of CO (up to 5 vol.%), demonstrating the benefits of thin-film-protected electrocatalysts. In general, this study provides insight into the synthesis and use of thin-film-protected electrodes leading to improvements in (electro)catalyst selectivity and durability

Ag-Functionalized CuWO₄/WO₃ nanocomposites for solar water splitting

Ag-Functionalized CuWO 4 /WO 3 heterostructures were successfully prepared via a polyvinyl pyrrolidone (PVP)-assisted sol-gel (PSG) route. Thin films prepared via electrophoretic deposition were used as photoanodes for photoelectrochemical (PEC) water splitting. Compared to pristine CuWO 4 and WO 3 films, a significant enhancement of the photocurrent (3-4 times) at the thermodynamic potential for oxygen evolution (0.62 V vs. Ag/AgCl, pH 7) was obtained for the Ag-functionalized CuWO 4 /WO 3 photoanodes. The obtained enhancement is shown to be derived from a synergic contribution of heterostructure formation (CuWO 4 /WO 3 ) and improvements of light utilization by Ag-induced surface plasmon resonance (SPR) effects. Accordingly, a photocurrent of 0.205 mA cm -2 at 0.62 V vs. Ag/AgCl under neutral conditions (without hole scavengers) under front-side simulated AM1.5G illumination was achieved. A detailed analysis of the obtained PEC data alongside performed impedance measurements suggests that charge seperation is significantly improved for the prepared Ag-functionalized CuWO 4 /WO 3 photoanodes. Our work offers beneficial insights to design new plasmonic metal/heterostructured nanocomposites for energy conversion applications

Photocatalytic Oxidation of Propane Using Hydrothermally Prepared Anatase-Brookite-Rutile TiO2 Samples. An In Situ DRIFTS Study

Photocatalytic oxidation of propane using hydrothermally synthesized TiO2 samples with similar primary crystal size containing different ratios of anatase, brookite and rutile phases has been studied by measuring light-induced propane conversion and in situ DRIFTS (diffuse reflectance Fourier transform infrared spectroscopy). Propane was found to adsorb on the photocatalysts, both in the absence and presence of light. The extent of adsorption depends on the phase composition of synthesized titania powders and, in general, it decreases with increasing rutile and brookite content. Still, the intrinsic activity for photocatalytic decomposition of propane is higher for photocatalysts with lower ability for propane adsorption, suggesting this is not the rate-limiting step. In situ DRIFTS analysis shows that bands related to adsorbed acetone, formate and bicarbonate species appear on the surface of the photocatalysts during illumination. Correlation of propane conversion and infrared (IR) data shows that the presence of formate and bicarbonate species, in excess with respect to acetone, is composition dependent, and results in relatively low activity of the respective TiO2. This study highlights the need for precise control of the phase composition to optimize rates in the photocatalytic oxidation of propane and a high rutile content seems to be favorable.This research was by funded by GV/FEDER (PROMETEO/2018/076), MICINN and FEDER (RTI2018-095291-B-I00), University of Alicante (VIGROB-136 and Mobility Grants from the EDUA to facilitate obtaining the title of International Doctor)

Electrochemically Induced pH Change: Time-Resolved Confocal Fluorescence Microscopy Measurements and Comparison with Numerical Model

Confocal fluorescence microscopy is a proven technique, which can image near-electrode pH changes. For a complete understanding of electrode processes, time-resolved measurements are required, which have not yet been provided. Here we present the first measurements of time-resolved pH profiles with confocal fluorescence microscopy. The experimental results compare favorably with a one-dimensional reaction-diffusion model; this holds up to the point where the measurements reveal three-dimensionality in the pH distribution. Specific factors affecting the pH measurement such as attenuation of light and the role of dye migration are also discussed in detail. The method is further applied to reveal the buffer effects observed in sulfate-containing electrolytes. The work presented here is paving the way toward the use of confocal fluorescence microscopy in the measurement of 3D time-resolved pH changes in numerous electrochemical settings, for example in the vicinity of bubbles.Comment: 10 pages, 7 figures, Supplementary informatio

Tailoring Mixed-Halide, Wide-Gap Perovskites via Multistep Conversion Process

Wide-band-gap mixed-halide CH3NH3PbI3–XBrX-based solar cells have been prepared by means of a sequential spin-coating process. The spin-rate for PbI2 as well as its repetitive deposition are important in determining the cross-sectional shape and surface morphology of perovskite, and, consequently, J–V performance. A perovskite solar cell converted from PbI2 with a dense bottom layer and porous top layer achieved higher device performance than those of analogue cells with a dense PbI2 top layer. This work demonstrates a facile way to control PbI2 film configuration and morphology simply by modification of spin-coating parameters without any additional chemical or thermal post-treatment

Back-illuminated Si-based photoanode with nickel cobalt oxide catalytic protection layer

Si is an excellent photo-absorber for use in dual-band-gap photoelectrochemical water splitting. We investigate photoanodes with n+pp+-Si configuration under back-side illumination, which is suited to work in a tandem device stack. A co-sputtered NiCoOx film coupled to the Si was used as a protective catalyst for the water oxidation reaction in 1 m KOH. The sample showed a high photocurrent (21 mA cm−2) under red-light illumination (38.6 mW cm−2). Long-term stability testing showed a gradual decrease of activity in the beginning, and then the activity increased, yielding a cathodic shift of the onset voltage (>50 mV), likely owing to the divergent response of Ni and Co to the Fe present in KOH. Once the activity of the sample stabilized, no further degradation was observed for the following 6 days, indicating that the demonstrated back-illuminated photoanode configuration can be considered a promising architecture for use as a bottom cell of the tandem water-splitting device under alkaline conditions