Photochromic mechanism in oxygen-containing yttrium hydride thin films: An optical perspective

Oxygen-containing yttrium hydride thin films exhibit photochromic behavior: Transparent thin films reversibly switch from a transparent state to a photodarkened state after being illuminated with UV or blue light. From optical spectrophotometry and ellipsometry measurements of the transparent state and photodarkened state, it is concluded that the photochromic effect can be explained by the gradual growth, under illumination, of metallic domains within the initial wide-band-gap semiconducting lattice. This conclusion is supported by Raman measurements

WO3/BiVO4: impact of charge separation at the timescale of water oxidation

The four hole oxidation of water has long been considered the kinetic bottleneck for overall solar-driven water splitting, and thus requires the formation of long-lived photogenerated holes to overcome this kinetic barrier. However, photogenerated charges are prone to recombination unless they can be spatially separated. This can be achieved by coupling materials with staggered conduction and valence band positions, providing a thermodynamic driving force for charge separation. This has most aptly been demonstrated in the WO3/BiVO4 junction, in which quantum efficiencies for the water oxidation reaction can approach near unity. However, the charge carrier dynamics in this system remain elusive over timescales relevant to water oxidation (μs–s). In this work, the effect of charge separation on carrier lifetime, and the voltage dependence of this process, is probed using transient absorption spectroscopy and transient photocurrent measurements, revealing sub-μs electron transfer from BiVO4 to WO3. The interface formed between BiVO4 and WO3 is shown to overcome the “dead-layer effect” encountered in BiVO4 alone. Moreover, our study sheds light on the role of the WO3/BiVO4 junction in enhancing the efficiency of the water oxidation reaction, where charge separation across the WO3/BiVO4 junction improves both the yield and lifetime of holes present in the BiVO4 layer over timescales relevant to water oxidation

WO3/BiVO4: impact of charge separation at the timescale of water oxidation

The four hole oxidation of water has long been considered the kinetic bottleneck for overall solar-driven water splitting, and thus requires the formation of long-lived photogenerated holes to overcome this kinetic barrier. However, photogenerated charges are prone to recombination unless they can be spatially separated. This can be achieved by coupling materials with staggered conduction and valence band positions, providing a thermodynamic driving force for charge separation. This has most aptly been demonstrated in the WO3/BiVO4 junction, in which quantum efficiencies for the water oxidation reaction can approach near unity. However, the charge carrier dynamics in this system remain elusive over timescales relevant to water oxidation (μs–s). In this work, the effect of charge separation on carrier lifetime, and the voltage dependence of this process, is probed using transient absorption spectroscopy and transient photocurrent measurements, revealing sub-μs electron transfer from BiVO4 to WO3. The interface formed between BiVO4 and WO3 is shown to overcome the “dead-layer effect” encountered in BiVO4 alone. Moreover, our study sheds light on the role of the WO3/BiVO4 junction in enhancing the efficiency of the water oxidation reaction, where charge separation across the WO3/BiVO4 junction improves both the yield and lifetime of holes present in the BiVO4 layer over timescales relevant to water oxidation

Solution-Processed Ni-Based Nanocomposite Electrocatalysts: An Approach to Highly Efficient Electrochemical Water Splitting

In this study, we report an up-scalable and low-cost solution-processed method to in situ synthesize an earth-abundant non-stoichiometric NiOx-based electrocatalytic film for water oxidation. The catalytic activity was found to be inversely proportional to the baking temperature, which varied from 50 to 500 °C. We found the formation of a hybrid nanocomposite thin film of NiOx nanocrystals (<2 nm size) inside an acetate-based organic matrix at low temperatures (<200 °C). The defective and short-range structural order of the NiOx-based nanocomposite electrocatalysts, compatible with lattice stress, low electrical conductivity, and high density of catalytically active surface species, and higher Fe incorporation were responsible for the enhanced electrocatalytic activity. Our champion NiOx catalyst features a 358 mV overpotential at 10 mA cm–2 and more than 60 h of continuous operation without significant losses, which is a remarkable milestone for undoped NiOx electrocatalysts synthesized at nearly room temperature by a solution-processed up-scalable method.Funding for open access charge: CRUE-Universitat Jaume IThe authors acknowledge the financial support from the Ministerio de Ciencia, Innovación y Universidades of Spain through funded projects ENE2017-85087-C3-1-R, RYC-2015-18349, and TEC2017-86102-C2-1-R and Agencia Valenciana de la Innovacion (AVI) INNVAL10/18/032. The authors thank the Central Support Service for Experimental Research (SCSIE) (XRD and SEM facilities) and the Institute of Materials Science (TGA and DTA equipment) of the University of Valencia and the Central Service of Scientific Instrumentation (SCIC) at University Jaume I. The authors also thank Prof. Juan P. Martinez-Pastor for his constructive suggestions and scientific discussions

Switchable All Inorganic Halide Perovskite Nanocrystalline Photoelectrodes for Solar-Driven Organic Transformations

All inorganic halide perovskite nanocrystals (NCs) are considered as fascinating materials for a wide range of optoelectronic applications encompassing photovoltaics, lasing, sensing, and photocatalysis due to their outstanding optoelectronic properties. Herein, it is demonstrated that the photoelectrochemical behavior of CsPbBr3 NC films can be tailored through engineering the selective contacts and accepting species in the electrolyte. This concept has been successfully applied to the photoelectrochemical oxidation of benzyl alcohol (BzOH) to benzyl aldehyde (BzCHO) and the reverse photoelectrochemical reduction of BzCHO to BzOH, demonstrating that CsPbBr3 NCs activate both reactions with photocurrents up to 40 μA cm 2 toward BzCHO production and 5 μA cm 2 for the reverse reaction at 0.15 V versus normal hydrogen electrode. The obtained results highlight the huge potential and versatility of halide perovskite NCs for photoelectrocatalytic applications, validating the implementation of these materials for a wide range of solar-driven complex organic transformations, and emphasizing the urgent need for stabilization strategies to move beyond the proof-of-concept stage to relevant technological developments

Impact of oxygen vacancy occupancy on charge carrier dynamics in BiVO4 photoanodes

Oxygen vacancies are ubiquitous in metal oxides and critical to performance, yet the impact of these states upon charge carrier dynamics important for photoelectrochemical and photocatalytic applications, remains contentious and poorly understood. A key challenge is the unambiguous identification of spectroscopic fingerprints which can be used to track their function. Herein, we employ five complementary techniques to modulate the electronic occupancy of states associated with oxygen vacancies in situ in BiVO4 photoanodes, allowing us to identify a spectral signature for the ionisation of these states. We obtain an activation energy of ̴ 0.2 eV for this ionisation process, with thermally activated electron de-trapping from these states determining the kinetics of electron extraction, consistent with improved photoelectrochemical performance at higher temperatures. Bulk, un-ionised states however, function as deep hole traps, with such trapped holes being energetically unable to drive water oxidation. These observations help address recent controversies in the literature over oxygen vacancy function, providing new insights into their impact upon photoelectrochemical performance

Experimental evidences of the direct influence of external magnetic fields on the mechanism of the electrocatalytic oxygen evolution reaction

The use of magnetic fields as external stimuli to improve the kinetics of electrochemical reactions is attracting substantial attention, given their potential to reduce energy losses. Despite recent reports showing a positive effect on catalytic performance upon applying a magnetic field to a working electrode, there are still many uncertainties and a lack of experimental evidence correlating the presence of the magnetic field to the electrocatalytic performance. Here, we present a combination of electrochemical and spectroscopic tools that demonstrate how the presence of an external magnetic field alters the reaction mechanism of the electrocatalytic oxygen evolution reaction (OER), accelerating the overall performance of a Ni4FeOx electrode. Complementary experimental evidence has been gathered supporting the participation of this microscopic magnetic field effect. Electrochemical impedance spectroscopy (EIS) points to a speed-up of the intrinsic reaction kinetics, independent of other indirect effects. In the same direction, the spectro-electrochemical fingerprint of the intermediate species that appear during the electrocatalytic cycle, as detected under operando conditions, indicates a change in the order of the reaction as a function of hole accumulation. All these experimental data confirm the direct influence of an external magnetic field on the reaction mechanism at the origin of the magnetically enhanced electrocatalytic OER