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Photoelectrocatalytic approaches show promise for contaminate removal in wastewater through redox reactions. However, the direct treatment of very low concentration heavy metals is a challenging task. Copper bismuth oxide is considered as a potential photocathode material due to its appropriate bandgap width and excellent light absorption properties. In this work, we utilize copper bismuth oxide photoelectrodes with micrometer-scale pores to achieve the efficient and complete reduction of micromolar-level hexavalent chromium(VI) in wastewater. In a continuous 180 min experiment, the reduction rate of 5 µM hexavalent chromium reached 97%, which is an order lower than the drinking standard. Such a process was facilitated by the unique hierarchical microstructure of the oxide thin film and the porous morphology. On the other hand, the structural evolution during the operation was analyzed. A surface passivation was observed, suggesting the possible long-term practical application of this material. This study serves as an important reference for the application of photoelectrocatalysis in addressing Cr(VI) pollution in wastewater, with implications for improving water quality and environmental protection. [ABSTRACT FROM AUTHOR]

The morphology of catalysts in microchannels plays a crucial role in the orbital maneuvering and networking applications of micro/nano satellites using hydrogen peroxide as a unit propellant. In this paper, a microfluidic reaction chip was designed and fabricated to detect the reaction rate of the catalytic decomposition of hydrogen peroxide solution by a microchannel catalytic bed. In addition, a silver thin film prepared by constant-current electroplating was used as a substrate for the microchannel catalyst. The results show that the ratio of surface area to area of silver film and the average particle size of silver particles have a significant positive correlation on the reaction rate of catalytic decomposition, while the thickness, silver content, and surface roughness of the silver film have no significant effect on the reaction rate of catalytic decomposition. The catalytic performance of the microchannel catalytic bed of silver thin film is greatly influenced by the conditions of electroplating, namely, the electroplating temperature (T), time (t), and current (I). And when I = 0.3 mA, t = 180 s, and T = 60 °C, the microchannel catalytic bed of the silver film prepared by electroplating reaches the optimal reaction rate for the catalytic decomposition of hydrogen peroxide solution. This study has the best process parameters for the design and optimization of heterogeneous catalysts applied to microfluidic reactors. [ABSTRACT FROM AUTHOR]

While the reverse water-gas shift (RWGS) reaction holds great promise as a method of converting CO2 to CO and subsequently into valuable fuels, achieving its commercial viability requires the development of highly efficient, selective, durable, and low-cost catalysts. Recently, thin-film nanocatalysts produced through plasma deposition (PECVD) have garnered significant attention in this domain. Among them, FeOx-based catalytic films deposited using Fe(CO)5 as a precursor, under reduced pressure (4–5 Pa) and a 13.56 MHz glow discharge, have demonstrated particular interest. Our study shows that by appropriately tuning the parameters of the plasma deposition process, it is feasible to generate nanocatalyst films exhibiting exceptional CO2 conversion (38% at 673 K) and CO selectivity (97%). Moreover, the study has revealed the formation of a carbon deposit containing carbon nanotubes (CNTs) during the RWGS reaction, significantly increasing the catalytic activity of the films. Through an analysis involving X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and electron microscopy techniques (SEM and HRTEM), we have determined that CNTs not only serve as carriers for highly catalytically active Fe nanoparticles but also create nanoscale heterojunctions (p-n) with Fe2O3 nanoparticles, thereby enhancing their catalytic effect. This paper attempts to elucidate the differences and changes in the surface structure of FeOx-based films dictating the catalytic activity, which stems from both the conditions of plasma deposition and the environmental impact during the catalytic process. [ABSTRACT FROM AUTHOR]

A quantum dot (QD) thin film of arsenic (III) oxide-hydroxide/polypyrrole (As2S3-As2O3/Ppy) with a supernova-like shape has been developed for optoelectronic applications across a wide optical range, spanning from ultraviolet (UV) to infrared (IR). The fabrication process involves the polymerization of pyrrole to form Ppy in the presence of NaAsO2 and K2S2O8. The resulting QD exhibits a remarkable morphology characterized by a supernova-like structure and a porous nature with a particle size of 4 nm. The unique morphology of the QD contributes to its optical properties. The material demonstrates a maximum optical absorbance that extends up to 600 nm. The chemical structure of the composite has been proved using various characterization techniques. The As2S3-As2O3/Ppy QD thin film holds significant potential for optoelectronic applications, particularly in light detection across multiple optical regions. Its sensitivity has been evaluated through the measurement of photoresponsivity (R), yielding a high value of 0.31 mA/W. This indicates a substantial current density (Jph) of 0.031 mA/cm2 at a wavelength of 340 nm. Additionally, the detectivity (D) of the photodetector has been calculated based on these values, resulting in a detection capability of 6.9 × 107 Jones. This indicates the ability to detect low levels of photons using this photodetector. The highly reproducible nature of this photodetector enables its application in various optoelectronic systems. The As2S3-As2O3/Ppy QD thin film offers great promise as a versatile optoelectronic application with its wide optical range, excellent sensitivity, and detectivity. [ABSTRACT FROM AUTHOR]

In this work, cuprous oxide (Cu2O) thin films were prepared using a simplistic sputtering technique. The films were grown on both traditional fluorine-doped tin oxide (FTO) and Ti-metallic substrates. X-ray diffraction applied for investigation of the crystal structure proved that the Cu2O layer acquires the cubic structure with a (111) main peak at 2θ of 36.46°. The optical absorption and transmission were detected through the utilization of a UV-Vis spectrophotometer, and the optical bandgap for the Cu2O layer was determined to be ~2.15 eV using Tauc's equation. XPS and scanning electron microscopy were also performed for chemical structure and morphological investigation, respectively. The optoelectronic behaviors for the prepared samples were carried out using a Keithley source meter; the photocurrent density was measured in a range of applied voltage between −1 and 1 volt under the illumination of a xenon lamp with a power density of 100 mWcm−2. External quantum efficiency, sensitivity, responsivity, and detectivity were computed using proprietary models based on the experimental data. [ABSTRACT FROM AUTHOR]

In this study, Pt-M/WO3 (M = Cu, Co, and Ni) thin films are effectively synthesized by preparing homogeneous precursor sols, spin-coating, toluene-etching, and calcination. Furthermore, the microstructural, chemical, and electrochemical properties of the WO3, Pt-Cu/WO3, Pt-Co/WO3, and Pt-Ni/WO3 thin films are also systematically compared. The results demonstrate that when compared to the WO3 thin film, the photocatalytic capability for methylene blue (MB) solution degradation is greatly increased in the Pt-M/WO3 thin films. Transfer routes for photogenerated charges and an improved photocatalytic process are suggested based on the experimental results. Due to the large difference in the work function (Φ) between the bimetallic alloy Pt-M and WO3, a bending of the energy bands at the Pt-M/WO3 interface is presented. Furthermore, the introduction of transition metals such as Cu, Co, or Ni modifies the electronic structure of Pt-M/WO3 thin films, facilitating the separation and migration of electrons and holes. Specifically, the photogenerated electrons migrate from the CB of WO3 to Pt-Co or Pt-Ni nanoparticles in the samples of Pt-Co/WO3 or Pt-Ni/WO3 thin films, while the hot electrons from the localized surface plasmon resonance (LSPR) effect of Cu could transfer to the conduction band (CB) of WO3 and other electrons generated from the photoexcitation of the WO3 semiconductor itself in the sample of the Pt-Cu/WO3 thin film. In summary, this work proposes a unique strategy for creating electron regulation in Pt-M decorated WO3 thin films for photocatalytic application. [ABSTRACT FROM AUTHOR]

The effects of the porosity and the thickness on the ability of hydrogen sensing is demonstrated through a comparison of compact and nanoporous platinum film sensors. The synthesis of anodic aluminum oxide (AAO) nanotubes with an average pore diameter of less than 100 nm served as the template for the fabrication of nanoporous Pt films using an anodization method. This was achieved by applying a voltage of 40 V in 0.4 M of a phosphoric acid solution at 20 °C. To compare the film and nanoporous Pt, layers of approximately 3 nm and 20 nm were coated on both glass substrates and AAO templates using a sputtering technique. FESEM images monitored the formation of nanoporosity by observing the Pt layers covering the upper edges of the AAO nanotubes. Despite their low thickness and the poor long-range order, the EDX and XRD measurements confirmed and uncovered the crystalline properties of the Pt films by comparing the bare and the Pt deposited AAO templates. The nanoporous Pt and Pt thin film sensors were tested in the hydrogen concentration range between 10–50,000 ppm H2 at room temperature, 50 °C, 100 °C and 150 °C. The results reveal that nanoporous Pt performed higher sensitivity than the Pt thin film and the surface scattering phenomenon can express the hydrogen sensing mechanism of the Pt sensors. [ABSTRACT FROM AUTHOR]

This work reports an innovative approach to the fabrication of free-standing thin films of multiwalled carbon nanotubes (MWCNTs)/graphene oxide (GO) nanohybrids by using dimethyl formamide (DMF) and n-hexane as a solvent–antisolvent system for the growth of thin films of MWCNTs/GO nanohybrids. The synthesis of the GO was carried out by using the modified Hummers method, while the synthesis of MWCNTs/GO nanohybrids was done by the intermixing of the carboxylic acid functionalized MWCNT and GO using the solution-mixing method. The growth of the thin film of MWCNTs/GO nanohybrids was done by obeying the surface-tension-driven phenomena which occur mainly due to the coalescence of bubbles due to the solvent–antisolvent interfacial tension. Furthermore, density functional theory (DFT)-based first-principles simulations were performed to understand the structural, electronic, and capacitive aspects of MWCNT/GO nanohybrids. The computational results demonstrated excellent quantum capacitance in the MWCNT/GO nanohybrid electrodes. Inspired by the computational results, the same process elaborated above has also been employed to develop binder-free supercapacitor devices utilizing the MWCNT/GO nanohybrid as an electrode material. The electrochemical performance of this electrode in 1 M aqueous H2SO4 demonstrates a good energy density of 21.63 WhKg−1 at a current density of 0.5 Ag−1, with a high specific capacitance of 369.01 F/g at the scan rate of 2 mVs−1 and excellent cyclic stability of 97% for 5000 charge–discharge cycles. [ABSTRACT FROM AUTHOR]

Carbon-protected BiVO4 photoanode and Cu2O photocathode tandem photoelectrochemical (PEC) system has been explored to reduce surface recombination and enhance the stability of the photoelectrodes. In addition to the carbon layer, the electrodeposited FeOOH nanolayer and drop-casted MoS2 co-catalyst layer on the photoanode and photocathode, respectively improve the reaction kinetics. The optimized photoanode (Mo-BiVO4/C/FeOOH) and photocathode (Cu2O/C/MoS2) produces current densities of ~1.22 mA cm−2 at 1.23 V vs. RHE and ~−1.48 mA cm−2 at 0 V vs. RHE, respectively. The obtained photocurrent is higher than bare photoelectrodes without a carbon layer. Finally, a tandem cell has been constructed, and an unassisted current density of ~0.107 mA cm−2 is obtained for a carbon-protected BiVO4–Cu2O tandem PEC cell at zero bias. The improved stability and enhanced photocurrent of the carbon protective layer are attributed to its better charge transfer resistance and minimized surface defects. Carbon protective layer can be a viable option to improve the stability of photoelectrodes in aqueous media. [ABSTRACT FROM AUTHOR]

Hollow cathode plasma sputtering is an advantageous method of preparing catalysts in the form of thin oxide films on supports. Such catalysts are particularly suitable for processes such as catalytic total oxidation of volatile organic compounds (VOCs), representing an economically feasible and environmentally friendly method of VOC abatement. Catalysts with Ni:Co molar ratios of 1:4, 1:1, and 4:1 were prepared on stainless-steel meshes and compared with single-component Ni and Co oxide catalysts. The properties of the catalysts were characterized by EDX, SEM, powder XRD, temperature-programmed reduction (H2-TPR), Raman spectroscopy, and XPS. Powder XRD revealed the formation of various crystalline phases that were dependent on molar the Ni:Co ratio. NiO and Co3O4 were identified in the single-component Ni and Co oxide catalysts, whereas Ni-Co mixed oxides with a spinel structure, together with NiO, were found in the catalysts containing both Ni and Co. Raman spectra of the catalysts prepared at high working pressures showed a slightly lower intensity of bands, indicating the presence of smaller oxide particles. The TPR profiles confirmed the improved reducibility of the Ni-Co oxide catalysts compared to the single-component Ni and Co catalysts. Catalytic activity was investigated in the deep oxidation of ethanol and toluene, which were used as model volatile organic compounds. In ethanol oxidation, the activity of sputtered catalysts was up to 16 times higher than that of the commercial Cu-Mn oxide catalyst EnviCat® VOC-1544. The main benefits of the sputtered catalysts are the much lower content of Ni and Co oxides and a negligible effect of internal diffusion. Moreover, the process of plasma jet sputtering can be easily implemented on a large scale. [ABSTRACT FROM AUTHOR]

Thermal vapor condensation of melamine at various temperatures was used to fabricate thin graphitic carbon nitride (g-C3N4) films on fluorine-doped tin oxide (FTO) coated glass substrates. Photoanodic (n-type) and photocathodic (p-type) responses were observed simultaneously in the g-C3N4 films. The g-C3N4 film formed at 520 °C with the longest average lifetime of the photo-excited electrons shows the best cathodic photocurrent performance, which was then chosen for electrochemical and photoelectrochemical reduction of CO2. When the basic electrolyte (CO2-saturated 0.5 M KHCO3, pH = 7.6) was adopted, CO2 was electrochemically converted into formaldehyde ((54.6 μM/h)) in the liquid product. When the acidic electrolyte (CO2-saturated 0.5 M KCl, pH = 4.1) was adopted, formaldehyde (39.5 μM/h) and ethanol (15.7 μM/h) were generated through photoelectrochemical reduction, stimulated by the presence of sufficient protons from the electrolyte in the reduction process. Therefore, the pure g-C3N4 film has a great potential for CO2 reduction to value-added liquid hydrocarbons products via electrochemical or photoelectrochemical ways. [ABSTRACT FROM AUTHOR]

In this work, tetra(4-carboxyphenyl)porphyrin (TCPP) and two Anderson-type polyoxomolybdates (containing Cu and Zn, respectively; CuPOM, ZnPOM) were synthesized and deposited on TiO2 thin films. The properties of the obtained materials were characterized through UV–vis spectroscopy, Fourier transform infrared spectroscopy (FT-IR), diffuse reflection spectroscopy, scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). The adsorption and photodegradation under the visible light irradiation of methylene blue (MB) were studied for TiO2, TCPP/TiO2, TCPP/CuPOM/TiO2 and TCPP/ZnPOM/TiO2 thin films in aqueous solution. The results of the diffuse reflectance showed two bands in the visible light spectrum for the TCPP/POM/TiO2 systems compared to unmodified TiO2 that does not show any bands in the same region of the spectrum. The TCPP/POM/TiO2 systems showed a higher removal of MB, with an adsorption rate near to 31% for the TCPP/CuPOM/TiO2 film compared to 9% adsorption on the TiO2 film. The kinetic results show that the pseudo-second order model was the best fitting model for the MB adsorption process onto fabricated materials. The photodegradation studies under visible light showed a better performance on TCPP/POM/TiO2 thin films, with an efficiency in the MB photodegradation of near 49% and 44% in aqueous solution for TCPP/CuPOM/TiO2 and TCPP/ZnPOM/TiO2, respectively. The reusability test indicated that the porphyrin films are moderately stable after the performed cycles. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Poly(ethylene 2,5-furanoate) (PEF) is arousing great interest as a biobased alternative to plastics like poly(ethylene terephthalate) (PET) due to its wide range of potential applications, such as food and beverage packaging, clothing, and in the car industry. In the present study, the hydrolysis of PEF powders of different molecular masses (Mn = 55, Mw = 104 kg/mol and (Mn = 18, Mw = 29 kg/mol) and various particle sizes (180 < d and 180 < d < 425 µm) using cutinase 1 from Thermobifida cellulosilytica (Thc_cut1) was studied. Thereby, the effects of molecular mass, particle size and crystallinity on enzymatic hydrolysis were investigated. The results show that particles with lower molecular mass are hydrolyzed faster than those with higher masses, and that the higher the molecular mass, the lower the influence of the particle size on the hydrolysis. Furthermore, cutinases from Humicola insolens (HiC) and Thc_cut1 were compared with regard to their hydrolytic activity on amorphous PEF films (measured as release of 2,5-furandicarboxylic acid (FDCA) and weight loss) in different reaction media (1 M KPO pH 8, 0.1 M Tris-HCl pH 7) and at different temperatures (50 ˚C and 65 ˚C). A 100% hydrolysis of the PEF films was achieved after only 72 h of incubation with a HiC in 1 M KPO pH 8 at 65 ˚C. Moreover, the hydrolysis reaction was monitored by LC/TOF-MS analysis of the released reaction products and by Scanning Electron Microscopy (SEM) examination of the polymer surfaces. Enzymatic hydrolysis of PEF with Thc_cut1 and HiC has potential for use in surface functionalization and recycling purposes. [ABSTRACT FROM AUTHOR]

Oxygen reduction is considered a key reaction for electrochemical energy conversion but slow kinetics hamper application in fuel cells and metal-air batteries. In this review, the prospect of perovskite oxides for the oxygen reduction reaction (ORR) in alkaline media is reviewed with respect to fundamental insight into activity and possible mechanisms. For gaining these insights, special emphasis is placed on highly crystalline perovskite films that have only recently become available for electrochemical interrogation. The prospects for applications are evaluated based on recent progress in the synthesis of perovskite nanoparticles. The review concludes with the current understanding of oxygen reduction on perovskite oxides and a perspective on opportunities for future fundamental and applied research. [ABSTRACT FROM AUTHOR]

In this work, we communicate a facile and low temperature synthesis process for the fabrication of graphene-TiO2 photocatalytic composite thin films. A sol-gel chemical route is used to synthesize TiO2 from the precursor solutions and spin and spray coating are used to deposit the films. Excitation of the wet films during the casting process by ultrasonic vibration favorably influences both the sol-gel route and the deposition process, through the following mechanisms. The ultrasound energy imparted to the wet film breaks down the physical bonds of the gel phase. As a result, only a low-temperature post annealing process is required to eliminate the residues to complete the conversion of precursors to TiO2. In addition, ultrasonic vibration creates a nanoscale agitating motion or microstreaming in the liquid film that facilitates mixing of TiO2 and graphene nanosheets. The films made based on the above-mentioned ultrasonic vibration-assisted method and annealed at 150°C contain both rutile and anatase phases of TiO2, which is the most favorable configuration for photocatalytic applications. The photoinduced and photocatalytic experiments demonstrate effective photocurrent generation and elimination of pollutants by graphene-TiO2 composite thin films fabricated via scalable spray coating and mild temperature processing, the results of which are comparable with those made using lab-scale and energy-intensive processes. [ABSTRACT FROM AUTHOR]

Galvanic replacement is the spontaneous replacement of surface layers of a metal, M, by a more noble metal, Mnoble, when the former is treated with a solution containing the latter in ionic form, according to the general replacement reaction: nM + mMnoble n+ → nMm+ + mMnoble. The reaction is driven by the difference in the equilibrium potential of the two metal/metal ion redox couples and, to avoid parasitic cathodic processes such as oxygen reduction and (in some cases) hydrogen evolution too, both oxygen levels and the pH must be optimized. The resulting bimetallic material can in principle have a Mnoble-rich shell and M-rich core (denoted as Mnoble(M)) leading to a possible decrease in noble metal loading and the modification of its properties by the underlying metal M. This paper reviews a number of bimetallic or ternary electrocatalytic materials prepared by galvanic replacement for fuel cell, electrolysis and electrosynthesis reactions. These include oxygen reduction, methanol, formic acid and ethanol oxidation, hydrogen evolution and oxidation, oxygen evolution, borohydride oxidation, and halide reduction. Methods for depositing the precursor metal M on the support material (electrodeposition, electroless deposition, photodeposition) as well as the various options for the support are also reviewed. [ABSTRACT FROM AUTHOR]

Studying catalysts in situ is of high interest for understanding their surface structure and electronic states in operation. Herein, we present a study of epitaxial manganite perovskite thin films (Pr1-xCaxMnO3) active for the oxygen evolution reaction (OER) from electro-catalytic water splitting. X-ray absorption near-edge spectroscopy (XANES) at the Mn L- and O K-edges, as well as X-ray photoemission spectroscopy (XPS) of the O1s and Ca 2p states have been performed in ultra-high vacuum and in water vapor under positive applied bias at room temperature. It is shown that under the oxidizing conditions of the OER a reduced Mn2+ species is generated at the catalyst surface. The Mn valence shift is accompanied by the formation of surface oxygen vacancies. Annealing of the catalysts in O2 atmosphere at 120 °C restores the virgin surfaces. [ABSTRACT FROM AUTHOR]

We report on the fabrication of sub-20 nm BiFeO3 (BFO) nanoparticles using a solid-state approach and preferential leching process. The nanoparticles were subsequently used to deposit, through spray pyrolysis, BFO thin films in a rhombohedral (R3c) crystallographic structure. Then, systematic investigations of the optical and the photocatalytic properties were conducted to determine the effects of the particles size, the microstructure and the increased surface area on their catalytic performances. Especially, improved optical properties were observed, with an optical bandgap energy of 2.20 eV compared to reported 2.7 eV for the bulk system. In addition, high optical absorption was obtained in the UV–visible light region reaching up to 90% at 400 nm. The photoelectrochemical measurements revealed a high photocurrent density under visible light irradiation. Besides, density functional theory calculations were performed on both bulk and thin film BFO structures, revealing an interesting comparison of the electronic, magnetic, ferroelectric and optical properties for bulk and thin film BFO systems. Both theoretical and experimental findings show that the alignment of the band edges of BFO thin film is coherent with good photocatalytic water splitting potential, making them desirable photoanode materials. [ABSTRACT FROM AUTHOR]

Over the past several decades, an increasing amount of attention has been given to catalytic combustion as an environmentally friendly process. However, major impediments to large-scale application still arise on the materials side. Here, we review catalytic combustion on thin film catalysts in view of highlighting some interesting features. Catalytic films open the way for new designs of structured catalysts and the construction of catalysts for catalytic combustion. A special place is occupied by materials in the form of very thin films that reveal catalytic activity for various chemical reactions. In this review, we demonstrate the high catalytic activity of thin film catalysts in these oxidation reactions. [ABSTRACT FROM AUTHOR]

Magnetron sputtering is an advantageous method for preparing catalysts supported on stainless steel meshes. Such catalysts are particularly suitable for processes carried out at high space velocities. One of these is the catalytic total oxidation of volatile organic compounds (VOC), economically feasible and environmentally friendly method of VOC abatement. The reactive radio frequency (RF) magnetron sputtering of Mn and Co + Mn mixtures in an oxidation Ar + O2 atmosphere was applied to form additional thin oxide coatings on cobalt oxide layers prepared by electrochemical deposition and heating on stainless steel meshes. Time of the RF magnetron sputtering was changed to obtain MnOx and CoMnOx coatings of various thickness (0.1–0.3 µm). The properties of the supported CoOx-MnOx and CoOx-CoMnOx catalysts were characterized by scanning electron microscopy (SEM), powder X-ray diffraction (XRD), temperature programmed reduction (H2-TPR), Fourier-transform infrared (FTIR) and Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The catalytic activity was investigated in the deep oxidation of ethanol, which was employed as a model VOC. According to the specific activities (amount of ethanol converted per unit mass of metal oxides per hour), the performance of CoOx-MnOx catalysts was higher than that of CoOx-CoMnOx ones. The catalysts with the smallest layer thickness (0.1 µm) showed the highest catalytic activity. Compared to the commercial pelletized Co-Mn-Al mixed oxide catalyst, the sputtered catalysts exhibited considerably higher (23–87 times) catalytic activity despite the more than 360–570 times lower content of the Co and Mn active components in the catalytic bed. [ABSTRACT FROM AUTHOR]

Thin films of Ca-doped double perovskite, PrBa0.7Ca0.3Co2O5+δ (PBCC), were epitaxially grown on (001) SrTiO3, and their redox reactions under a switching flow of H2 and O2 gases were examined at various temperatures by measuring the resistance R(t) of the films as a function of the gas flow time t. In the temperature range between 350 and 725 °C, these thin films are reduced and oxidized in an ultrafast manner under the flow of H2 and O2 gases, respectively, suggesting that PBCC thin films are promising candidates for developing ultra-sensitive oxygen sensors or SOFC cathodes at intermediate or high temperatures. When the gas flow is switched to O2, the reduced PBCC thin films exhibit a negative resistance at temperatures above 600 °C but a positive resistance at temperatures below 600 °C. The probable cause for these anomalous transport properties is the diffusion of the H atoms from the cathode to the anode in the PBCC film, which provides a current opposite to that resulting from the external voltage. [ABSTRACT FROM AUTHOR]

A pure Ti target in Ar/O2 gas mixture was used to synthesize Ti3Ox thin film on a glass substrate by Reactive High-Power Impulse Magnetron Sputtering (HiPIMS) under different sputtering power (2 and 2.5 kW). The influence of HiPIMS parameters on thin films' structural, morphological, chemical composition, optical and photocatalytic, and antibacterial properties was investigated. In this study, Ti3Ox thin films can be synthesized using the HiPIMS method without the post-annealing process. Two co-existence phases (hexagonal Ti3O and base-centered monoclinic Ti3O5 phases) existed on the Ti3Ox films. It is found that the peak intensity of (006) Ti3O hexagonal slightly increased as the sputtering power increased from 2 to 2.5 kW. The Ti3Ox thin-film bandgap values were 3.36 and 3.50 eV for 2 and 2.5 kW, respectively. The Ti3Ox films deposited at 2.5 kW showed good photocatalytic activity under UV light irradiation, with a higher methylene blue dye degradation rate than TiO2 thin films. The antibacterial study on Ti3Ox thin films exhibited a high inhibition percentage against E. coli and S. aureus. This study demonstrates that Ti3Ox thin films can promote high photocatalytic and antibacterial activity. [ABSTRACT FROM AUTHOR]

Titanium dioxide (TiO2) is widely used, studied, and synthesized using different methodologies. By a modification of the material, it can be applied to wastewater treatment. A combined sputtering-laser ablation setup was used to deposit TiO2 thin films modified, individually and simultaneously, with gold (Au) and silver (Ag). To investigate the effect of the metal incorporation in titanium and its impact on the photocatalytic activity, with dye discoloration as a pollutant compound model, the deposited films were characterized by UV–Vis, photoluminescence, and Raman spectroscopies, as well as by parallel beam X-ray diffraction. The results showed that films with different Au and Ag loads, and an 18 nm average crystallite size, were obtained. These metals have an essential effect on the deposited film's compositional, structural, and optical properties, directly reflected in its photocatalytic activity. The photocatalytic test results using UV-Vis showed that, after 1 h of applying a 4.8 V electric voltage, a discoloration of up to 80% of malachite green (MG) was achieved, using ultraviolet (UV) light. [ABSTRACT FROM AUTHOR]

Photocatalytic water splitting into hydrogen is considered as one of the key solutions to the current demand for eco-responsible energy. To improve the efficiency and sustainability of this process, the development of a TiO2-based photoanode by adding bio-sourced surfactants to the sol–gel preparation method has been considered. Three different polymeric biosurfactants (GB, GC, and BIO) have been tested, giving rise to three different materials being structurally and morphologically characterized by XRD, Rietveld refinement, BET, SEM, AFM, and XPS, which was completed by light absorption, photocatalytic (Pilkington test), electronic (EIS and C-AFM), and photoelectrochemical (cyclic voltammetry) measurements. Correlations between the structure/morphology of materials and their functional properties have been established. One specific surfactant has been proven as the most suitable to lead to materials with optimized photoelectrochemical performance in direct relation with their photocatalytic properties essentially controlled by their specific surface area. [ABSTRACT FROM AUTHOR]

The growing level of wastewater as well as pollution of freshwater by various bacteria are essential worldwide issues which have to be solved. In this contribution, nanocrystalline anatase TiO2 films deposited by magnetron sputtering on high-density polystyrene (HDPE) beads were applied as floating photocatalysts for Salmonella typhimurium bacterial inactivation in water for the first time. Additionally, the photocatalytic degradation of methylene blue dye in the presence of HDPE beads with TiO2 film under UV-B irradiation was investigated. The suitability to adopt such floating photocatalyst structures for practical applications was tested in cycling experiments. The detailed surface morphology, crystal structure, elemental mapping, surface chemical composition and bond analysis of deposited TiO2 films were investigated by scanning electron microscope, X-ray diffractometer and X-ray photoelectron spectroscope techniques. The bacterial viability as well as MB decomposition experiments showed promising results by demonstrating that 6% of bacterial colonies were formed after the first run and only about 1% after the next four runs, which is an appropriate outcome for practical applications. NPN uptake results showed that the permeability of the outer membrane was significantly increased as well. [ABSTRACT FROM AUTHOR]

Different percentages of CuO and ZnO were added into a local kaolin ceramic-based powder (DD3) with and without ZrO2. The modified powders were first characterized, then, a test for the photocatalytic degradation of dyes with orange II (OII) was carried out. The DD3 powders that were obtained with the addition of ZrO2, ZnO, and CuO, were prepared by two different methods and have shown a large and very fast photocatalytic activity. Discoloration ratios of about 93.6% and 100% were reached after 15 min and 45 min, for CuO and ZnO respectively. Finally, an alternative photocatalysis mechanism, based purely on chemical reaction processes, is proposed. The photocatalysis results with modified powders are compared with the results obtained with thin films, made with the same materials. [ABSTRACT FROM AUTHOR]

The preparation of tungsten oxide (WO3) thin film by direct current (DC) reactive sputtering magnetron method and its photoelectrocatalytic properties for water oxidation reaction are investigated using ultraviolet-visible radiation. The structural, morphological, and compositional properties of WO3 are fine-tuned by controlling thin film deposition time, and post-annealing temperature and environment. The findings suggest that the band gap of WO3 can be controlled by adjusting the post-annealing temperature; the band gap decreased from 3.2 to 2.7 eV by increasing the annealing temperature from 100 to 600 °C. The theoretical calculations of the WO3 bandgap and the density of state are performed by density functional theory (DFT). Following the band gap modification, the photoelectrocatalytic activity increased and the maximum photocurrent (0.9 mA/cm2 at 0.6 VSCE) is recorded with WO3 film heated at 500 °C. The WO3 film heated under air exhibits much better performance in photoelectrochemical water oxidation process than that of annealed under inert atmosphere, due to its structural variation. The change in sputtering time leads to the formation of WO3 with varying film thickness, and the maximum photocurrent is observed when the film thickness is approximately 150 nm. The electrical conductivity and charge transfer resistance are measured and correlated to the properties and the performance of the WO3 photoelectrodes. In addition, the WO3 photoelectrode exhibits excellent photoelectrochemical stability. [ABSTRACT FROM AUTHOR]

Thin films of metallic rhodium (Rh) are developed on two different supports, nickel foam (NF) and titanium foil (Ti), and evaluated for electrochemical hydrogen evolution reaction (HER). The electrodes are prepared by aerosol-assisted chemical vapor deposition technique using a Rh diethyldithiocarabamte precursor for three distinct time periods of 40, 80, and 120 min at 500 °C. The film consists of phase pure metallic Rh with hierarchical flower-like morphology. The structural features of such nanostructures can be modulated by adjusting the growth time. The HER catalytic performance data for the optimized films (i.e., with the deposition time of 80 min) suggest that the Rh deposited on Ti foil (Rh/Ti) catalyze the reaction substantially faster than Rh deposited on Ni foam (Rh/NF). To produce current density of 100 mA cm−2, the Rh/NF needed over potential of 263 mV, while the Rh/Ti electrode required only 175 mV. In spite of lower electrical conductivity, caused by the bare Ti foil, the Rh/Ti electrode exhibits superior HER performance. The Tafel slopes of Rh/NF and Rh/Ti electrodes are determined to be 52 and 42 mV dec−1, while the turnover frequencies are estimated to be 1.1 and 37.3 s−1 at over potential of 260 mV. [ABSTRACT FROM AUTHOR]

This review presents an update describing binary and ternary semiconductors involving interfacial charge transfer (IFCT) in composites made up by TiO2, CuO, Ag2O and Fe2O3 used in microbial disinfection (bacteria and viruses). The disinfection mechanism, kinetics and generation of reactive oxygen species (ROS) in solution under solar/visible light are discussed. The surface properties of the photocatalysts and their active catalytic sites are described in detail. Pathogenic biofilm inactivation by photocatalytic thin films is addressed since biofilms are the most dangerous agents of spreading pathogens into the environment. [ABSTRACT FROM AUTHOR]

Titanium dioxide (TiO2) has been widely used as a catalyst material in different applications such as photocatalysis, solar cells, supercapacitor, and hydrogen production, due to its better chemical stability, high redox potential, wide band gap, and eco-friendly nature. In this work TiO2 thin films have been deposited onto both glass and silicon substrates by the atmospheric pressure plasma jet (APPJ) technique. The structure and morphological properties of TiO2 thin films are studied using different characterization techniques like X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and field emission scanning electron microscopy. XRD study reveals the bronze-phase of TiO2. The XPS study shows the presence of Ti, O, C, and N elements. The FE-SEM study shows the substrate surface is well covered with a nearly round shaped grain of different size. The optical study shows that all the deposited TiO2 thin films exhibit strong absorption in the ultraviolet region. The oleic acid photocatalytic decomposition study demonstrates that the water contact angle decreased from 80.22 to 27.20° under ultraviolet illumination using a TiO2 photocatalyst. [ABSTRACT FROM AUTHOR]

Pure titanium dioxide TiO2 photocatalytic substrates exhibit antibacterial activity only when they are irradiated with ultraviolet light, which comprises high-energy wavelengths that damage all life. Impurity doping of TiO2-related materials enables visible light to stimulate photocatalytic activity, which enhances opportunities for TiO2 to be used as a disinfectant in living environments. Boron-doped TiO2 displays visible-light-responsive bactericidal properties. However, because boron-derived compounds also exert notable antibacterial effects, most reports did not clearly demonstrate the extent to which the bactericidal property of boron-doped TiO2 is contributed by visible-light-stimulated photocatalysis. In addition, TiO2 thin films have considerable potential for applications in equipment that requires sterilization; however, the antibacterial properties of boron-doped TiO2 thin films have been examined by only a few studies. We found that boron-doped TiO2 thin films displayed visible-light-driven antibacterial properties. Moreover, because boron compounds may have intrinsic antibacterial properties, using control groups maintained in the dark, we clearly demonstrated that visible light stimulated the photocatalysis of boron-doped TiO2 thin films but not the residue boron compounds display antibacterial property. The bactericidal effects induced by visible light are equally potent for the elimination of the model organism Escherichia coli and human pathogens, such as Acinetobacter baumannii, Staphylococcus aureus, and Streptococcus pyogenes. The antibacterial applications of boron-doped TiO2 thin films are described, and relevant perspectives discussed. [ABSTRACT FROM AUTHOR]

N- and Ni-coated TiO2 (NNT) were prepared by a facile sol-gel method as a photosensitive photocatalyst to visible light. NNT sol was used to coat the surface of an LED lamp cap and body made of polycarbonate with a thin NNT film. The coated thin film was dried in an oven at 130 °C. This NNT thin film had an amorphous TiO2 structure and absorbed 600 nm of visible light. The decomposition properties of formaldehyde on the NNT photocatalyst after irradiation with visible light were investigated. The LED lamp was irradiated with visible light at 500–620 nm and 6 W. Formaldehyde was decomposed by a photocatalytic reaction by visible light irradiation on the NNT-coated polycarbonate surface. Escherichia coli (E. coli), Staphylococcus aureus, and Pseudomonas aeruginosa were also used to examine the sterilizing properties of pathogenic bacteria using an LED lamp kit. The pathogenic bacteria on the NNT-coated polycarbonate surface were sterilized by irradiation with visible light. [ABSTRACT FROM AUTHOR]

Molybdenum sulphide is an emerging precious-metal-free catalyst for cathodic water splitting. As its active sites catalyse the Volmer hydrogen adsorption step, it is particularly active in acidic media. This study focused on the electrochemical deposition of MoS2 on copper foam electrodes and the characterisation of their electrocatalytic properties. In addition, the electrodeposition was modified by adding a reducing agent—sodium hypophosphite—to the electrolyte. To reveal the role of hypophosphite, X-ray photoelectron spectroscopy (XPS) analysis was carried out in addition to scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). MoS2 films, electrodeposited at various charges passed through the cell (catalyst loadings), were tested for their catalytic activity towards hydrogen evolution in 0.5 M H2SO4. Polarisation curves and Tafel slope analysis revealed that the electrodeposited MoS2 films are highly active. Namely, Tafel slopes fell within the 40–50 mV dec−1 range. The behaviour of as-deposited films was also evaluated by electrochemical impedance spectroscopy over a wide overpotential range (0 to −0.3 V), and two clear time constants were distinguished. Through equivalent electrical circuit analysis, the experimental data were fitted to the appropriate model, and the obtained values of the circuit components were examined as a function of overpotential. It was found that the addition of NaH2PO2 into the electrodeposition solution affects the intrinsic activity of the material. Finally, a method is proposed to approximate the number of active sites from impedance data. [ABSTRACT FROM AUTHOR]

Carbon fiber has been extensively used in the photocatalysis, electrocatalysis and energy storage fields as supporting platform and conductive media. However, less attention has been paid with regards to its function in phonon transport and thermal management. We have investigated the effect of current flow direction on the heat management performance of carbon fiber based thin film heaters (CFTFHs) with anisotropic percolation network of carbon fibers (CFs). The anisotropic percolation network of carbon fibers (CFs) formed by roll-to-roll spray coating leads to the anisotropic electrical properties of CFs. As a result, CFs based thin films (CFTFs) have lower sheet resistance when measured parallel to the CFs alignment, compared to when they are aligned perpendicular. Because connectivity and current flow in CFs are critically dependent on the direction alignment of CFs, the saturation temperature (106.4 °C) of CFTFH with parallel aligned carbon fiber is higher than that (117.3 °C) of CFTFH with perpendicular alignment. Therefore, current flow in the same direction as the alignment of CFs is very important to achieve high-performance. Moreover, our study on thermal profile of anisotropic CFTFs under high current flows illustrates that carbon fiber thin films have great potential in thermal management solution for electrocatalytic and electrochemical energy storage applications. [ABSTRACT FROM AUTHOR]

In this study, TiO2 thin films were deposited by ultrasonic spray pyrolysis from solutions with concentrations of 0.1 and 0.2 M. The deposition temperature was adjusted at 350 °C and all samples were annealed at 500 °C for 1 h in air. The thickness of TiO2 films was changed in the range of 50 to ca. 800 nm by varying the number of spray cycles from 1 to 21 and the solution concentration. The results showed that the mean crystallite size of the anatase structure, the surface roughness, and light absorption increased with the film thickness. The effect of film thickness on the photocatalytic activity was investigated with the photodegradation of stearic acid under UV-A irradiation. The optimal thickness of TiO2 films fabricated by ultrasonic spray pyrolysis for photocatalytic self-cleaning applications was in the range of 170–230 nm, indicating a ca. 2.6 times-higher photocatalytic self-cleaning activity compared to the reference sample, Pilkington ActivTM. The photocatalytic results showed that the 190 nm-thick TiO2 film deposited from the 0.1 M solution applying seven spray cycles exhibited the finest grain structure and maximum photocatalytic activity, leading to 94% of stearic acid degradation in 180 min under UV-A light with the reaction rate constant k = 0.01648 min−1. [ABSTRACT FROM AUTHOR]

TiO2 thin films, modified by acetylacetone (AcacH) in solution, were deposited on glass substrate by ultrasonic spray pyrolysis and tested for photocatalytic activity in a multi-section continuous flow reactor by degradation of acetone and acetaldehyde under ultraviolet and visible light. The increase in molar ratio of AcacH in respect of titanium (IV) isopropoxide (TTIP) from 1:5 to 1:8 modified the electronic structure of the films, favoring enhanced photocatalytic activity. The photocatalytic activity was enhanced approximately twofold on the film with molar ratio 1:8 under both irradiations; the film completely oxidized 10 ppm of acetone and acetaldehyde. The photocatalytic efficacy of TiO2 films in oxidation of air pollutants was three times higher compared to the industrial glass Pilkington ActivTM. Moreover, all the synthesized films indicate antibacterial efficiency against E. coli of over 99% under ultraviolet. TiO2 film, with TTIP:AcacH molar ratio 1:8 having great possibility for its commercial use as a material for indoor air purification. [ABSTRACT FROM AUTHOR]

Alloys of platinum and lanthanides present a remarkable activity for the oxygen reduction reaction—both in the form of extended surfaces and nanoparticulate catalysts. Co-sputter-deposited thin film catalysts based on platinum and gadolinium show great oxygen reduction activity improvement over pure Pt. The sputter-deposition technique represents a viable and versatile approach for investigating model catalyst systems with different compositions. In this work, co-sputtered Pt5Gd and Pt7.5Gd thin films were investigated using X-ray absorption spectroscopy as well as standardized electrochemical techniques. These investigations revealed the importance of forming alloys with specific stoichiometry, supporting the need of forming compressively strained Pt overlayers in order to achieve optimum catalytic performances. [ABSTRACT FROM AUTHOR]

The aim of the presented investigations was to deposit the thin films La1−xSrxFeO3 (x = 0, 0.1, 0.2) on (100) Si substrate by using the Pulsed Laser Deposition (PLD) method. Structure was exanimated by using XRD, SEM, AFM, TEM and XPS methods. The catalytic properties were analyzed in 4 ppm acetone atmosphere. The doping of Sr thin films La1−xSrxFeO3 (x = 0, 0.1, 0.2) resulted in a decrease in the size of the crystallites, the volume of the elemental cell and change in the grain morphology. In the LaFeO3 and La0.9Sr0.1FeO3, clusters around which small grains grow are visible in the structure, while in the layer La0.8Sr0.2FeO3, the visible grains are elongated. The TEM analysis has shown that the obtained thin films had a thickness in the range 150–170 nm with triangular or flat column ends. The experiment performed in the presence of gases allowed us to conclude that the surfaces (101/020) in the triangle-shaped columns and the plane (121/200) faces in flat columns were exposed to gases. The best properties in the presence of CH3COCH3 gas were noted for LaFeO3 thin film with triangle columns ending with orientation (101/020). [ABSTRACT FROM AUTHOR]

Titanium dioxide (TiO2) thin films are used for a broad range of applications such as wastewater treatment, photocatalytic degradation activity, water splitting, antibacterial and also in biomedical applications. There is a wide range of synthesis techniques for the deposition of TiO2 thin films, such as chemical vapor deposition (CVD) and physical vapor deposition (PVD), both of which are well known deposition methods. Layer by layer deposition with good homogeneity, even thickness and good adhesive nature is possible by using the PVD technique, with the products being used for photocatalytic applications. This review studies the effects of magnetron sputtering conditions on TiO2 films. This innovative technique can enhance the photocatalytic activity by increasing the thickness of the film higher than any other methods. The main purpose of this article is to review the effects of DC and RF magnetron sputtering conditions on the preparation of TiO2 thin films for photocatalysis. The characteristics of TiO2 films (i.e., structure, composition, and crystallinity) are affected significantly by the substrate type, the sputtering power, the distance between substrate and target, working pressure, argon/oxygen ratio, deposition time, substrate temperature, dopant types, and finally the annealing treatment. The photocatalytic activity and optical properties, including the degree of crystallinity, band gap (Eg), refractive index (n), transmittance (T), and extinction coefficient (k), of TiO2 films are dependent on the above- mentioned film characteristics. Optimal TiO2 films should have a small particle size, a strong degree of crystallinity, a low band gap, a low contact angle, a high refractive index, transmittance, and extinction coefficient. Finally, metallic and nonmetallic dopants can be added to enhance the photocatalytic activity of TiO2 films by narrowing the band gap. [ABSTRACT FROM AUTHOR]

We synthesized and characterized both Co-doped ZnO (ZnO:Co) and Cu-doped ZnO (ZnO:Cu) thin films. The catalysts' synthesis was carried out by the sol–gel method while the doctor blade technique was used for thin film deposition. The physicochemical characterization of the catalysts was carried out by Raman spectroscopy, scanning electron microscopy (SEM), X-ray diffraction, and diffuse reflectance measurements. The photocatalytic activity was studied under visible irradiation in aqueous solution, and kinetic parameters were determined by pseudo-first-order fitting. The Raman spectra results evinced the doping process and suggested the formation of heterojunctions for both dopants. The structural diffraction patterns indicated that the catalysts were polycrystalline and demonstrated the presence of a ZnO wurtzite crystalline phase. The SEM analysis showed that the morphological properties changed significantly, the micro-aggregates disappeared, and agglomeration was reduced after modification of ZnO. The ZnO optical bandgap (3.22 eV) reduced after the doping process, these being ZnO:Co (2.39 eV) and ZnO:Co (3.01 eV). Finally, the kinetic results of methylene blue photodegradation reached 62.6% for ZnO:Co thin films and 42.5% for ZnO:Cu thin films. [ABSTRACT FROM AUTHOR]

Converting water into hydrogen through the photo-electrochemical (PEC) process is one of the most exciting approaches in this field, and there is a quest to design or search for new electro-photo-catalytic materials. In this work, simple steps for fabrication and transformation of metallic tungsten thin film into the photo-active Magnéli-phase (W18O49) of tungsten oxide thin film is demonstrated. The post-annealing temperature has a significant impact on the phase evolution of tungsten film into W18O49. The film thickness of W18O49 is controlled by controlling the sputtering time (or deposition time) of W film. The PEC performance of the as-prepared electrodes is evaluated by monitoring the water oxidation reaction under visible radiation. The PEC findings reveal a correlation between PEC performance and phase, morphology, and thickness of the film. The as-derived W18O49 can efficiently catalyze the water oxidation reaction at neutral solution pH, generating 0.6 and 1.4 mA cm−1 photo-current at 0.6 and 0.8 V vs. Saturated calomel electrode (SCE), respectively, in addition to excellent stability. The electrical conductivity and the charge transfer kinetics are investigated employing the electrochemical impedance spectroscopic (EIS) technique. [ABSTRACT FROM AUTHOR]

Black TiO2 materials have been quite widely explored due to their large solar absorption and superior photocatalytic activity. In this paper, the blackening process of titanium dioxide (TiO2) thin film using the hollow cathode hydrogen plasma (HCHP) technique is reported. First, pristine anatase TiO2 films were grown by magnetron sputtering onto silicon and cover glass substrates and then annealed at 450 °C for 2 h. Then, the as-grown TiO2 films were treated with HCHP for 15 min. The physical, chemical and morphological properties of the films were analyzed by profilometry, X-ray diffraction (XRD), UV-Vis spectrophotometry, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) techniques. Electrical and photocatalytic measurements were performed by four-point probe and methylene blue UV degradation assays, respectively. The results showed that the black TiO2 film is highly absorbent in the UV-visible region, has low electrical resistance and greater surface area compared to the non-treated TiO2 film. These properties of black TiO2 film, as well as its performance as a photocatalytic agent, were investigated, indicating the superior quality of this material in thin film form and the promising potential of the HCHP treatment to produce hydrogenated TiO2 in short process time. [ABSTRACT FROM AUTHOR]

Plasma-enhanced chemical vapor deposition (PECVD) was used to produce new Ru-based thin catalytic films. The surface molecular structure of the films was examined by X-ray photoelectron spectroscopy (XPS). To determine the electro- and photoelectrochemical properties, the oxygen evolution reaction (OER) process was investigated by linear sweep voltammetry (LSV) at pH = 13.6. It was found that Ru atoms were mainly in the metallic state (Ru0) in the as-deposited films, whereas after the electrochemical stabilization, higher oxidation states, mainly Ru+4 (RuO2), were formed. The stabilized films exhibited high catalytic activity in OER—for the electrochemical process, the onset and η10 overpotentials were approx. 220 and 350 mV, respectively, while for the photoelectrochemical process, the pure photocurrent density of about 160 mA/cm2 mg was achieved at 1.6 V (vs. reversible hydrogen electrode (RHE)). The plasma-deposited RuOX catalyst appears to be an interesting candidate for photoanode material for photoelectrochemical (PEC) water splitting. [ABSTRACT FROM AUTHOR]

Atomic layer deposition (ALD) is a special type of chemical vapor deposition (CVD) technique that can grow uniformed thin films on a substrate through alternate self-limiting surface reactions. Recently, the application of these thin film materials to catalytic systems has begun to attract much attention, and the capacity to deposit these catalytic films in a highly controlled manner continues to gain importance. In this study, IrO2 and NiO thin films (approximately 25 to 60 nm) were deposited on industrial Ni expanded mesh as an anode for alkaline water electrolysis. Different ALD operating parameters such as the total number of deposition cycles, sublimation and deposition temperatures, and precursors pulse and purge lengths were varied to determine their effects on the structure and the electrochemical performance of the thin film materials. Results from the electrochemical tests (6 M KOH, 80 °C, up to 10 kA/m2) showed the catalytic activity of the samples. Oxygen overpotential values (ηO2) were 20 to 60 mV lower than the bare Ni expanded mesh. In summary, the study has demonstrated the feasibility of using the ALD technique to deposit uniformed and electroactive thin films on industrial metallic substrates as anodes for alkaline water electrolysis. [ABSTRACT FROM AUTHOR]

We studied the structural and morphological evolution of Rh clusters on an ordered ultrathin alumina film grown on NiAl(100) in annealing processes, under ultrahigh vacuum conditions and with various surface probe techniques. The Rh clusters, prepared on vapor deposition of Rh onto the alumina film at 300 K, had an fcc phase and grew in the (100) orientation; the annealing altered the cluster structure little—the lattice parameter decreased by a factor <2%—but the cluster morphology significantly. With elevated temperature, small clusters (diameter ≤1.5 nm) decreased little in size; in contrast, large clusters (diameter ≥2.0 nm) varied in a complex manner—their mean diameter decreased to about 1.5 nm on annealing to 450 K, despite their similar height, while it increased to above 2.0 nm at temperature ≥570 K. This atypical decrease in size was governed predominantly by energetics. Such a reduced size enhanced the total surface area as well as the reactivity of the clusters toward methanol decomposition, so increased the production of D2 (H2) and CO from decomposed methanol-d4 (or methanol). The result implies a higher temperature tolerance for Rh clusters on the alumina film and a practical approach to prepare small Rh clusters with high reactivity. [ABSTRACT FROM AUTHOR]

In this study, we deposited TiO2 thin films onto borosilicate glass by ultrasonic spray pyrolysis at 350 and 450 °C. The aim of study is to determine the effect of deposition temperature on photocatalytic activity of TiO2 thin films and to investigate the performance of TiO2 thin films on photocatalytic degradation of methyl tert-butyl ether (MTBE), acetone, acetaldehyde, and heptane as functions of different operating parameters. TiO2 thin films deposited at 350 and 450 °C have a thickness value of 190 and 330 nm, respectively. All as-prepared TiO2 films possess an anatase crystalline structure. According to the X-ray photon spectroscopy (XPS) study, the TiO2 thin film deposited at 350 °C showed a higher amount of oxygen vacancies and hydroxyl groups on the film surface after UV treatment. The aged-TiO2 thin film deposited at 350 °C showed a water contact angle (WCA) value of 0° after 10 min UV irradiation, showing superhydrophilic surface behavior. The TiO2 film deposited at 350 °C exhibited the highest amount of conversion of MTBE (100%). The results also showed that TiO2 films are capable of photocatalytic degradation of MTBE (100%) and acetaldehyde (approx. 80%) in humid air conditions and high airflow rate. The visible-light-activity of TiO2 thin films was tested with 5 ppm MTBE and acetone. TiO2 thin films deposited at 350 °C with a surface area of 600 cm2 showed 60% of MTBE and 33% of acetone degradation under VIS light. [ABSTRACT FROM AUTHOR]

Catalytic total oxidation is an effective procedure to minimize emissions of volatile organic compounds (VOC) emissions in industrial gases. Catalysts in the form of meshes are remarkable as they minimize the internal diffusion of reactants during the reaction as well as the need of expensive active components. In this paper, various conditions of radio frequency magnetron sputtering of cobalt on stainless-steel meshes was applied during catalyst preparation. Properties of the supported Co3O4 catalysts were characterized by SEM, XRD, temperature programmed reduction (H2-TPR), FTIR, XPS, and Raman spectroscopy. Catalytic activity was examined in deep oxidation of ethanol chosen as a model VOC. Performance of the catalysts depended on the amount of Co3O4 deposited on the supporting meshes. According to specific activities (the amounts of ethanol converted per unit weight of Co3O4), smaller Co3O4 particle size led to increased catalytic activity. The catalyst prepared by sputtering in an Ar+O2 atmosphere without calcination showed the highest catalytic activity, which decreased after calcination due to enlargement of Co3O4 particles. However, specific activity of this catalyst was more than 20 times higher than that of pelletized commercial Co3O4 catalyst used for comparison. [ABSTRACT FROM AUTHOR]

Diverse methods have been employed to synthesize MoS2 and MoSe2 catalyst systems. Herein, a combined photoelectrochemical (PEC) deposition and rapid-thermal annealing process has first been employed to fabricate MoS2 and MoSe2 thin films on Si substrates. The newly developed transition-metal dichalcogenides were characterized by scanning electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. PEC hydrogen evolution reaction (HER) was demonstrated in an acidic condition to show a PEC catalytic performance order of MoOx/Si < MoS2/Si << MoSe2/Si under the visible light-on condition. The HER activity (4.5 mA/cm2 at −1.0 V vs Ag/AgCl) of MoSe2/Si was increased by 4.8× compared with that under the dark condition. For CO2 reduction, the PEC activity was observed to be in the order of MoS2/Si < MoOx/Si << MoSe2/Si under the visible light-on condition. The reduction activity (0.127 mA/cm2) of MoSe2/Si was increased by 9.3× compared with that under the dark condition. The combined electrochemical deposition and rapid-thermal annealing method could be a very useful method for fabricating a thin film state catalytic system perusing hydrogen production and CO2 energy conversion. [ABSTRACT FROM AUTHOR]