Solvothermal synthesis of Mg-Ni/C nanocomposite for hydrogen storage using vitamin C as carbon source

Metal alloys such as Mg₂Ni and TiFe can absorb and store H₂ to form metal hydrides. The alloys are frequently prepared by grinding the metal ingredients together. In this work, a solvothermal synthesis was taken to prepare the Mg-Ni/C nanocomposite from vitamin C, magnesium acetate, and nickel acetate, using ethylene glycol as solvent and reductant. Without adding Pd as nucleating agent, it is proposed to obtain Mg-Ni alloys by reduction and carbon nanoparticles by carbonization. XRD analysis shows that Mg₂Ni and Mg-Ni₂ have been formed as nanocomposite with carbon. After calcination in vacuum at 500 °C for 1 h, the Mg-Ni/C nanocomposite showed enhanced magnetism. XRD results give peaks of Ni and MgO, indicative of phase separation and Mg oxidation. In conclusion, it is feasible to synthesize Mg-Ni/C or other carbon-containing hydrogen storage composites using the solvothermal method.     

Optical property and cycling durability of polytetrafluoroethylene top-covered and metal buffer layer inserted Mg-Ni switchable mirror

Pd-capped Mg-rich Mg-Ni alloy thin film shows excellent reversible switching properties in optical transmittance by the exposure to hydrogen containing gas. However, it shows fast degradation due to the oxidization of magnesium and the switching durability is not good enough for practical applications. To resolve this problem we tried to improve its switching durability of Mg-Ni based switchable mirror by the combined use of metal buffer layer insertion between Pd and Mg-Ni layer and polytetrafluoroethylene (PTFE) protective coating. PTFE thin film has been prepared on the surface of Mg-Ni thin films by RF magnetron sputtering in the Ar and CF₄ mixed gas discharge plasma at room temperature and a power of 30 W. The sample of Pd/Ti/Mg₄Ni thin film with the protective coating of 900-nm-thick PTFE layer can be switched over 1600 switching cycles, which suppress the degradation by 15% of its initial transmission modulation level.     

Preparation and characterization of CuInS2 thin films solar cells with large grain

The CuInS₂ films with a maximum thickness of about 9 μm and a maximum atomic Cu/In ratio (as-deposited precursor) of 3.0 were prepared, and, to prevent peeling from substrate, were heat treated during Cu/In evaporation and/or intercalated with very thin Pt or Pd (between Mo and CuInS₂ layers). Thus, we could prepare the films with very large grain. It is also worth noting that the large grain films were easily optimized by chemical etching of the films using a thick film and Cu-rich composition. Therefore, the absorber for high-efficiency solar cells can be prepared by varying over a wide range of composition and thickness of precursor. The characterization of CuInS₂ absorbers with various film thickness and compositions were investigated and related with the performance of the photovoltaic device.     

Oxidative photoelectrochemical technology with Ti/TiO2 anodes

Rutile and anatase TiO₂ films have been grown on Ti plates by thermal (500–800°C) and anodic oxidation followed by thermal annealing (400–500°C), respectively. The photoelectrochemical efficiency of these photoanodes, evaluated by current density measurements in the photooxidation of 4-methoxybenzyl alcohol in deaerated CH₃CN, has been determined. The photocurrent efficiency increases with the thickness of the TiO₂ rutile film up to 1 μm (the most efficient thickness). At the wavelengths furnished by the irradiation apparatus similar thicknesses of anatase and rutile films show nearly the same efficiencies. Anodic bias produces similar relative increases of current intensity in both crystalline forms.     

Improved CIGS thin-film solar cells by surface sulfurization using In2S3 and sulfur vapor

Surface sulfurization of Cu(In,Ga)Se₂ (CIGS) thin films was carried out using two alternative techniques that do not utilize toxic H₂S gas; a sequential evaporation of In₂S₃ after CIGS deposition and the annealing of CIGS thin films in sulfur vapor. A Cu(In,Ga) (S,Se)₂ thin layer was grown on the surface of the CIGS thin film after sulfurization using In₂S₃, whereas this layer was not observed for CIGS thin films after sulfurization using sulfur vapor, although a trace quantity of S was confirmed by AES analysis. In spite of the difference in the surface modification techniques, the cell performance and process yield of the ZnO:Al/CdS/CIGS/Mo/glass thin-film solar cells were remarkably improved by using both surface sulfurization techniques.     

Influence of H2S concentration on the properties of Cu2ZnSnS4 thin films and solar cells prepared by sol-gel sulfurization

Cu₂ZnSnS₄ (CZTS) thin films prepared by a non-vacuum process based on the sulfurization of precursor coatings, consisting of a sol-gel solution of Cu, Zn, and Sn, under H₂S+N₂ atmosphere were investigated. The structure, microstructure, and electronic properties of the CZTS thin films as well as solar cell parameters were studied in dependence on the H₂S concentration. The sulfurization process was carried out at 500 °C for 1 h in an H₂S+N₂ mixed-gas atmosphere with H₂S concentrations of 3%, 5%, 10%, and 20%. As the H₂S concentration decreased from 20% to 5%, the S content of the CZTS thin films decreased. However, when the H₂S concentration was decreased below 3%, the S content of the films began to increase. A CZTS thin film prepared with an H₂S concentration of 3% had grains in the order of 1 μm in size, which were larger than those of films prepared at other H₂S concentrations. Furthermore, the most efficient solar cell, with a conversion efficiency of 2.23%, was obtained from a sample sulfurized at an H₂S concentration of 3%.     

High performance hydrogen sensor based on Pd/TiO2 composite film

Hydrogen sensors with fast response and recovery rate based on nanoporous palladium (Pd) and titanium dioxide (TiO₂) composite films supported by anodic aluminum oxide (AAO) template have been demonstrated. Nanoporous TiO₂ film was sprayed on the porous AAO templates, followed by Pd film deposited on TiO₂ layer by DC magnetron sputtering. We have researched the detection performance of the hydrogen sensors depending on different thickness of TiO₂ layer from 6 to 30 nm with keeping the thickness of Pd as 30 nm. The results have demonstrated the sensors with 10 nm thickness of TiO₂ achieve the best performance with a response/recovery time as short as 4/8s at 0.8% and 0.4% hydrogen concentration, respectively. The sensors exhibited very good performance under hydrogen concentrations from 0.4% to 1.8%.     

Physically and chemically synthesized TiO2 composite thin films for hydrogen production by photocatalytic water splitting

TiO₂ thin films have been synthesized by radio-frequency magnetron sputtering and sol–gel method to study the hydrogen generation by photocatalytic water splitting under visible light irradiation. Photoelectrochemical cell with chemical bias, involving photo-anode in form of TiO₂ film deposited on conducting indium tin oxide (ITO) film and Pt as cathode, is developed. The effect of conducting ITO layer on photo-voltage is studied by varying the thickness of ITO films. Constant H₂ generation rate is obtained for long period of time by both the TiO₂ films because of the separated evolution of H₂ and O₂ gas, thus eliminating the back-reaction effect. Sputter-deposited film as compared to sol–gel-synthesized film showed better H₂ generation rate, mainly explained in terms of the higher visible light absorption achieved by oxygen vacancies created in the TiO₂ film by the energetic target ions during deposition in pure Ar gas pressure.     

Transformation of amorphous iron oxide thin films predeposited by spray pyrolysis into a single FeSe2-phase by selenisation

The present paper investigates a simple and non-toxic method to transform amorphous iron oxide pre-deposited by spray pyrolysis of FeCl₃·6H₂O (0.03 M)-based aqueous solution onto glass substrates heated at 350 °C into FeSe₂ thin films. The amorphous iron oxide films were heat treated under a selenium atmosphere (10⁻⁴ Pa) at different temperatures for 6 h. X-ray diffraction (XRD) was used to investigate the structure of the obtained films. Single FeSe₂-phase films having good crystallinity were obtained at a selenisation temperature of 550 °C. Optical analyses of the FeSe₂ films obtained at 550 °C enabled us to deduce a large absorption coefficient (, ). Surface scanning electron microscopy (SEM) observations show inhomogeneous films. Electrical conductivity of the as-prepared films was measured at high and low temperatures.     

The influence of hydrogen in the incorporation of Zn during the growth of Cu2ZnSnS4 thin films

Cu₂ZnSnS₄ (CZTS) is a p-type semiconductor, candidate to replace Cu(In,Ga)Se₂ as absorber layer in thin film solar cells. The best solar cells based on CZTS present efficiencies up to 6.8%. These results were improved when metallic Zn was replaced by ZnS, which may imply a different chemical path for the formation of CZTS. In this study it is compared with the diffusion of Zn on Cu₂SnS₃ by introducing metallic Zn or ZnS. For this CZTS films were grown by sulphurization of Cu₂SnS₃, some with a Zn layer and others with a ZnS layer. The influence of H₂ during the annealing process is also studied and for this some sulphurizations were done in the presence of a partial atmosphere of H₂.The SEM micrographs of the samples show a columnar growth structure of the films with different degrees of compactness. The compactness is improved in the samples where a ZnS layer was present in the precursor and the sulphurization was done in the presence of H₂. EDS chemical profiling revealed regular zinc distribution for the samples with metallic Zn whilst the ones with ZnS exhibited a Zn-rich surface. X-ray diffraction (XRD) indicated the presence of CZTS and Cu_2−xS phases in all samples. These results were confirmed by Raman scattering.It was concluded that the sulphurization of Cu₂SnS₃ films with the use of ZnS layers under H₂ atmosphere produces better quality CZTS thin films, since it promotes Zn diffusion and avoids Zn losses by evaporation.     

CO2 methanation combined with NH3 decomposition by in situ H2 separation using a Pd membrane reactor

Combination of the reactions by means of membrane separation techniques are of interest. The CO₂ methanation was combined with NH₃ decomposition by in situ H₂ separation through a Pd membrane. The CO₂ methanation reaction in the permeate side was found to significantly enhance the H₂ removal rate of Pd membrane compared to the use of sweep gas. The reaction rate of CO₂ methanation was not influenced by H₂ supply through the Pd membrane in contrast to NH₃ decomposition in the retentate side. However, the CH₄ selectivity could be improved by using a membrane separation technique. This would be caused by the active dissociated H species which might immediately react with adsorbed CO species on the catalysts to CH₄ before those CO species desorbed. From the reactor configuration tests, the countercurrent mode showed higher H₂ removal rate in the combined reaction at 673 K compared to the cocurrent mode but the reaction rate in CO₂ methanation should be improved to maximize the perfomance of membrane reactor.     

Optical properties of sol–gel dip-coated Ta2O5 films for electrochromic applications

Amorphous Ta₂O₅ films were prepared by sol–gel dip process on different substrates. The dip-coating technique was used to prepare amorphous Ta₂O₅ films by hydrolysis and condensation of tantalum ethoxide, Ta(OC₂H₅)₅, precursor. Stable coating solutions were prepared using acetic acid as a chelating ligand and catalyzer. Single layer and multi-layered Ta₂O₅ films were fabricated at a dipping rate of 107 mm/min. The microstructure, stoichiometry and optical properties of these films were investigated as a function of the film thickness. Room temperature CV measurements clearly revealed a protonic conductor behavior for Ta₂O₅ films. Optical properties such as refractive index, extinction coefficient and optical band gap value of the Ta₂O₅ films were calculated from optical transmittance measurements. It was found that the refractive index and extinction coefficient values were affected by the thickness of the coatings. The refractive index at a wavelength of 550 nm increased from 1.70 to 1.72 with increasing film thickness. The optical band gap value (3.75±0.12 eV) of the coating was unaffected by the film thickness. These results indicate that sol–gel-deposited Ta₂O₅ films have a promising application as proton conductors in electrochromic devices.     

The role of the substrate on the mechanical and thermal stability of Pd thin films during hydrogen (de)sorption

In this work, we studied the mechanical and thermal stability of ~100 nm Pd thin films magnetron sputter deposited on a bare oxidized Si(100) wafer, a sputtered Titanium (Ti) intermediate layer, and a spin-coated Polyimide (PI) intermediate layer. The dependence of the film stability on the film morphology and the film-substrate interaction was investigated. It was shown that a columnar morphology with elongated voids at part of the grain boundaries is resistant to embrittlement induced by the hydride formation (α?β phase transitions). For compact film morphology, depending on the rigidity of the intermediate layer and the adherence to the substrate, complete transformation (Pd-PI-SiO₂/Si) or partly suppression (Pd-Ti-SiO₂/Si) of the α to β-phase was observed. In the case of Pd without intermediate layer (Pd-SiO₂/Si), buckling delamination occurred. The damage and deformation mechanisms could be understood by the analysis of the stresses and dislocation (defects) behavior near grain boundaries and the film-substrate interface. From diffraction line-broadening combined with microscopy analysis, we showed that in Pd thin films, stresses relax at critical stress values via different relaxation pathways depending on film-microstructure and film-substrate interaction. On the basis of the in-situ hydriding experiments, it was concluded that a Pd film on a flexible PI intermediate layer exhibits free-standing film-like behavior besides being strongly clamped on a stiff SiO₂/Si substrate.     

Hydrogen gettering of titaniumpalladium/palladium nanocomposite films synthesized by cosputtering and vacuum-annealing

Nano-engineered composite film, prepared by the combination of titanium (Ti) nanoparticles with surrounding layers of palladium (Pd), has been suggested as a high performance hydrogen (H₂) getter. Uniform TiPd film covered by a 35-nm-thick Pd layer was deposited on a silicon wafer via cosputtering and post-vacuum-annealing. As the annealing temperature increased from 200 to 400 °C, amorphous alloy and nano-aggregates were observed, and efficient structural modulation occurred at 400 °C, where dewetting of Pd cover layer from the getter surface was observed. This led to the enhancement of the chemisorption capacity of the 400^oC-annealed sample, two-times higher than that of the 300^oC-annealed sample. Abrupt change in residual gases, which typically come from a bonding process, can be mitigated by minimizing the gas transfer distance through the dewetting of the cover layer; since Ti nanoparticles surrounded by Pd exist independently of each other in the gettering layer, external H₂ gas molecules can be continuously adsorbed onto still-unreacted Ti particles by passing through the dewetted channels in the Pd cover layer. This concept demonstrates a pathway towards a useful synthetic approach for high-performance thin-film getters with high adsorption capacity, fast gettering rate and good device compatibility.     

Study of electron-beam evaporated Sn-doped In2O3 films

Electron beam evaporated Sn-doped In₂O₃ films have been prepared from the starting material with composition of (1 − x) In₂O₃ − -x SnO₂, where x = 0.0, 0.010, 0.025, 0.050, 0.090, and 0.120. X-ray photoelectron spectroscopy, Rutherford backscattering spectrometry, and X-ray diffraction analysis were carried out on the films. Luminous transmittance and electrical resistivity of the films, show weak dependence on x. The composition of the film ([Sn]/[In] atomic ratio) was found to differ from that of the starting material. In fact, the atomic ratio was higher in the film than in the starting material by a factor which increases with x (ranging from 1.0 to 2.6). There is a relatively broad resistivity minimum in the layer atomic ratio range Sn/In = 0.06 − -0.09. These results compare well with those reported in the literature for Sn-doped In₂O₃ films, prepared by pyrolitic (spray) method.     

Ga homogenization by simultaneous H2Se/H2S reaction of Cu-Ga-In precursor

The compositional distribution of Ga and S in Cu(InGa)(SeS)₂ films fabricated by a simultaneous selenization and sulfization process was systematically investigated. At low H₂Se/H₂S reaction temperature (490 °C), most Ga remains at the back of the film adjacent to the Mo back contact. However, the Ga/III ratios at the top and bottom of the Cu(InGa)(SeS)₂ layer monotonically increase and decrease with reaction temperatures, respectively. At T>550 °C, homogeneous distribution of elemental Ga and In through film is achieved. Further increase of the reaction temperature (e.g., T>550 °C) causes phase segregation on the surface of the Cu(InGa)(SeS)₂ film confirmed by XRD, GIXRD and EDS analysis.     

Role of CO2 in the CH4 oxidation and H2 formation during fuel-rich combustion in O2/CO2 environments

The effect of CO₂ reactivity on CH₄ oxidation and H₂ formation in fuel-rich O₂/CO₂ combustion where the concentrations of reactants were high was studied by a CH₄ flat flame experiment, detailed chemical analysis, and a pulverized coal combustion experiment. In the CH₄ flat flame experiment, the residual CH₄ and formed H₂ in fuel-rich O₂/CO₂ combustion were significantly lower than those formed in air combustion, whereas the amount of CO formed in fuel-rich O₂/CO₂ combustion was noticeably higher than that in air. In addition to this experiment, calculations were performed using CHEMKIN-PRO. They generally agreed with the experimental results and showed that CO₂ reactivity, mainly expressed by the reaction CO₂ + H → CO + OH (R1), caused the differences between air and O₂/CO₂ combustion under fuel-rich condition. R1 was able to advance without oxygen. And, OH radicals were more active than H radicals in the hydrocarbon oxidation in the specific temperature range. It was shown that the role of CO₂ was to advance CH₄ oxidation during fuel-rich O₂/CO₂ combustion. Under fuel-rich combustion, H₂ was mainly produced when the hydrocarbon reacted with H radicals. However, the hydrocarbon also reacted with the OH radicals, leading to H₂O production. In fact, these hydrocarbon reactions were competitive. With increasing H/OH ratio, H₂ formed more easily; however, CO₂ reactivity reduced the H/OH ratio by converting H to OH. Moreover, the OH radicals reacted with H₂, whereas the H radicals did not reduce H₂. It was shown that OH radicals formed by CO₂ reactivity were not suitable for H₂ formation. As for pulverized coal combustion, the tendencies of CH₄, CO, and H₂ formation in pulverized coal combustion were almost the same as those in the CH₄ flat flame.     

Efficient H2 production by water-splitting using indium–tin-oxide/V-doped TiO2 multilayer thin film photocatalyst

In order to sensitize TiO₂ in visible light and to reduce photo-induced charge recombination, the multilayer films of Indium-Tin Oxide (ITO)/V-doped TiO₂ were synthesized by radio-frequency magnetron sputtering. V-doped TiO₂ thin films showed red shift in TiO₂ absorption edge with increasing dopant concentration and, most importantly, the dopant energy levels are formed in the TiO₂ band gap due to V⁵⁺/V⁴⁺ ions as confirmed by UV-Visible and XPS spectra. Multilayer films with different numbers of ITO/V-doped TiO₂ (6 at.%) bilayers (namely, 2-, 3-, 4-, 5-, 6- and 7-bilayers) were deposited, in order to reduce the charge recombination rate, by keeping the total thickness of TiO₂ constant in each multilayer film. In multilayer films, when exposed to visible light the photocurrent increases as function of the number of bilayers by reaching the maximum with 6-bilayers of ITO/V-doped TiO₂. The measured enhanced photocurrent is attributed to: 1) ability of V-doped TiO₂ to absorb visible light, 2) number of space-charge layers in form of ITO/TiO₂ interfaces in multilayer films, and 3) generation of photoelectrons just in/or near to the space-charge layer by decreasing the V-doped TiO₂ layer thickness. The reduced charge recombination rate in multilayer films was also confirmed by the photocurrent kinetic curves. The superior photocatalytic efficiency of the 6-bilayers film is also reflected in hydrogen production rate through water-splitting: we obtained indeed 31.2 μmol/h of H₂ production rate.     

Palladium nanoparticle deposition onto the WO3 surface through hydrogen reduction of PdCl2: Characterization and gasochromic properties

Nowadays, gasochromic Pd/WO₃ coatings as optically switchable materials have become more applicable for hydrogen sensors and smart windows. In this study, WO₃ films were prepared by Pulsed Laser Deposition (PLD) and spin-coating sol-gel techniques. For deposition of Pd, first a layer of PdCl₂ was obtained via a simple drop-drying process by dropping PdCl₂ solution onto WO₃ substrates and drying them at room temperature. Then Pd nanoparticles were synthesized via hydrogen gas exposure that causes reduction of the PdCl₂ layer. According to Scanning Electron Microscope (SEM) observations before hydrogen reduction, many individual nanoparticles or fractal-like constructions of palladium were formed in the PdCl₂ layer in which the fractal branches were distorted after hydrogen treatment. Surface chemistry of the observed Pd nanoparticles was studied using X-ray Photoelectron Spectroscopy (XPS) at different stages of the reduction process. The results showed that after hydrogen treatment, the chlorine atoms were desorbed from the PdCl₂ layer and a metallic Pd layer remained on the surface of WO₃. Gasochromic properties in the presence of H₂ or O₂ gases for different PdCl₂ amounts revealed that the rate and saturated level of coloring depends on the PdCl₂ amounts as well as on the preparation method of the WO₃ substrates due to different porosities.     

Plasma-assisted co-evaporation of β-indium sulfide thin films

This paper describes the development of plasma-assisted co-evaporation (PACE) for the formation of β-In₂S₃ thin films. Indium was supplied by conventional thermal evaporation, while the chalcogen gas precursor (H₂S) was activated using an inductively coupled plasma (ICP) source. Using a combination of optical emission spectroscopy and mass spectrometry it was shown that the ICP effectively dissociated H₂S, producing atomic sulfur. Transport modeling was used to quantify the flux distributions of the co-evaporated metal and the plasma-generated species impinging the substrate. Model predictions were validated by measurements of deposition rate and film properties. Substantial improvements in both materials utilization and substrate temperature reduction were realized with respect to conventional co-evaporation. β-In₂S₃ was formed as low as 100 °C and it was observed that quality was a strong function of S/In ratio. The grain size decreased and the optical band gap increased as the substrate temperature was reduced.