Continuous hydrogen production activity over finely dispersed Ag2O/TiO2 catalysts from methanol:water mixtures under solar irradiation: A structure–activity correlation

Ag₂O/TiO₂ catalysts with varying amounts of Ag₂O 0.5, 1, 2, and 5 wt% loadings are prepared by impregnation method and Ag/TiO₂ catalyst is prepared by photo deposition method. These catalysts are characterized by XRD, SEM-EDAX, DRS, XPS and TEM techniques. DRS studies clearly showing the expanded photo response of TiO₂ into visible region on impregnation of Ag⁺ ions on surface layers of TiO₂ due to the increased number of energy states created by the silver ions in TiO₂ surface lattice. TEM images are showing the fine dispersion of silver particles on TiO₂ surface. XPS of Ag₂O/TiO₂ calcined and used catalysts along with Ag₂O/TiO₂ reduced and Ag/TiO₂ photo deposited catalysts are compared and the binding energy values of Ti 2p, O1s and Ag 3d are confirming that silver ions are in interaction with TiO₂ in Ag₂O/TiO₂ calcined catalysts. EDAX analysis supports the presence of silver species on the surface layers of TiO₂. Photocatalytic hydrogen production activity studies are conducted over Ag₂O/TiO₂, Ag₂O/TiO₂ reduced and Ag/TiO₂ photo deposited catalysts in pure water and methanol:water mixtures under solar irradiation. Maximum hydrogen production of 145 μmoles/h is observed on 0.5wt% Ag₂O/TiO₂ catalyst in pure water and the maximum hydrogen production of 3350 μmoles/h is observed on 1wt% Ag₂O/TiO₂ catalyst in methanol:water mixtures. Whereas Ag₂O/TiO₂ reduced and Ag/TiO₂ photo deposited catalysts are not showing any hydrogen production activity either in water or in methanol:water mixtures under solar irradiation. Based on the XPS, DRS, TEM, SEM-EDAX studies and the hydrogen production activity on these catalysts, a structure–activity correlation has been proposed wherein the interacted Ag⁺ ions on the surface layers of TiO₂ are playing an important role in maintaining the hydrogen production activity under solar irradiation.     

Solvothermal synthesis ZnS–In2S3–Ag2S solid solution coupled with TiO2−xSx nanotubes film for photocatalytic hydrogen production

ZnS–In₂S₃–Ag₂S solid solution coupled with TiO_2-xS_x nanotubes film catalyst has been successfully prepared by a two-step process of anodization and solvothermal methods for the first time. The as-prepared photo-catalysts are characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), UV–Visible diffuse reflectance spectra (UV–Vis DRS), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS), respectively. The results show that the ZnS–In₂S₃–Ag₂S solid solution are deposited on the surface of TiO₂NTs nanotubes under the solvothermal conditions, by which S atoms are incorporated into the lattice of TiO₂ through substituting the sites of oxygen atoms. Such ZnS–In₂S₃–Ag₂S@TiO_2-xS_x nanotubes composite presents the enhanced absorption in visible region and the efficient transfer of photoelectron between the solid solution and TiO_2-xS_x nanotubes, which determines the excellent photocatalytic activity for the photocatalytic hydrogen evolution from aqueous solutions containing the sacrificial reagents of Na₂S and Na₂SO₃ under 500 W Xe lamp irradiation.     

Synthesis and characterization of , and hydrogen production from methanol photodecomposition over the mixture of and

This study focused on the production of hydrogen from the methanol destruction in a liquid photocatalytic system that comprised a mixture of Ag_xO and TiO₂ (P-25, Degussa). The nanometer particles of Ag_xO were obtained by a conventional sol–gel method in the presence of tetraethylammonium hydroxide using thermal treatment at 50, 100, 150, 200, 250, and to attain various silver oxide forms. The 38.0 and 43.0 peaks, which were assigned to Ag₂O and Ag metal, respectively, were seen in Ag_xO powder at each temperature; however, these Ag₂O/Ag ratios varied and the AgO form was not found in any of the samples. In the XPS data, the peak which was assigned to Ag3d_5/2 in the Ag metal or Ag₂O was present in all the Ag_xO samples. In particular, the peak of Ag3d_5/2 in the Ag metal was dominant at high temperature, while the peak of Ag3d_5/2 in Ag₂O increased at low temperature. When TiO₂ was used as a photocatalyst in the methanol photodecomposition reaction, no hydrogen gases were evolved. However, the hydrogen product was remarkably increased in the mixture of Ag_xO and TiO₂ photo-system. Moreover, it was more enhanced when Ag_xO thermally treated at was added, compared to the samples with Ag_xO thermally treated at other temperatures, and the production peaked at 17,000 μmol after 24 h.     

Enhancing the activity of a SiC–TiO2 composite catalyst for photo-stimulated catalytic water splitting

In this work, effort has been made to design an efficient catalyst for the photo-stimulated water splitting reaction, starting with the modification of TiO₂ (P25) to enhance its activity. A SiC(1 wt%)–TiO₂ composite material shows an activity as high as twice of that of TiO₂. NiO_x, an electron collector, promotes the activity of TiO₂, while IrO₂, a hole capturer, enhances the hydrogen evolution rate of SiC. A SiC(1 wt%)–NiO_x/TiO₂ three-component and an IrO₂/SiC(1 wt%)–NiO_x/TiO₂ four-component composite materials produce 30% and 100% more H₂ than the NiO_x/TiO₂ catalyst during the first 5 h, respectively, with ethanol used as the sacrificial reagent. Furthermore, the SiC(1 wt%)–NiO_x/TiO₂ catalyst is active under visible light, while the NiO_x/TiO₂ catalyst shows no activity under the same irradiation condition. 3C-SiC has a narrow band gap and its band edge well compensates that of the TiO₂. The enhancing effect of dopants on the SiC(1 wt%)–TiO₂ composite material is sensitive to the location of the modifiers, which further proves that an efficient separation of the charge carriers is crucial to the overall activity of the composite catalyst.     

Enhanced desorption properties of LiBH4 incorporated into mesoporous TiO2

LiBH₄ nano-particles are incorporated into mesoporous TiO₂ scaffolds via a chemical impregnation method. And the enhanced desorption properties of the composite have been investigated. The LiBH₄/TiO₂ sample starts to release hydrogen at 220 °C and the maximal desorption peak occurs at about 330 °C, much lower compared to the bulk LiBH₄. Furthermore, the composite exhibits excellent dehydrogenation kinetics, with 11 wt% of hydrogen liberated from LiBH₄ at 300 °C within 3 h. X-ray diffraction and Fourier transform infrared spectroscopy are used to confirm the nanostructure of LiBH₄ in the TiO₂ scaffold. This work demonstrates that confinement within active porous scaffold host is a promising approach for enhancing hydrogen decomposition properties of light-metal complex hydrides.     

Nanocrystallites-forming hierarchical porous Ni/Al2O3–TiO2 catalyst for dehydrogenation of organic chemical hydrides

Dehydrogenation of organic chemical hydrides has been improved by reconstructing the catalyst in the form of hierarchical porous structure nanocatalyst, in which the economical Ni was adopted as catalytic component and nano Al₂O₃–TiO₂ hybrid composite as support. The Al₂O₃–TiO₂ composite was prepared by spontaneous self-assembly of nano Al₂O₃ and TiO₂ aggregates by hydrolysis of tetra-n-butyl-titanate under continuous agitation. The multi-scaled distribution of Al₂O₃–TiO₂ aggregates with hierarchy could be observed in dynamic light scattering spectrometer. The aggregates are comprised of nano-sized γ-Al₂O₃ and anatase TiO₂ crystallites with sizes of about 5 and 7 nm, respectively. The surface modulation by TiO₂ could be verified in FTIR Spectra. The migration of Ti species and crystallite growth were hindered by the Al₂O₃ skeleton and the hierarchical porous structure was sustained during the thermal related process. The multi-scaled distributed pores were confirmed by both TEM analysis and N₂ adsorption results. The results of dehydrogenation experiments showed that the hierarchical porous structure nano Ni/Al₂O₃–TiO₂ exhibited superior catalytic performance to Ni/Al₂O₃ with the optimum conversion of 99.9% at 400 °C, while the catalyst of Ni/Al₂O₃ exhibited only 16.5% under the same condition.     

Cu(OH)2-modified TiO2 nanotube arrays for efficient photocatalytic hydrogen production

Cu(OH)₂/TNAs photocatalyst was prepared by loading Cu(OH)₂ nanoparticles on TiO₂ nanotube arrays (TNAs) using a chemical bath deposition method. The amount of Cu(OH)₂ loaded on the arrays was controlled by the repeated deposition times. The prepared catalyst was used to generate hydrogen under simulated solar light irradiation, and the results demonstrated that the hydrogen yield of Cu(OH)₂/TNAs was 20.3 times that of the pure TNAs. Furthermore, the photocatalytic efficiency for hydrogen production decreased only 5.8% after five cycles, indicating that Cu(OH)₂/TNAs photocatalyst showed excellent stability and reusability. This work presents an applicable and facile method to fabricate a highly active and stable photocatalyst for hydrogen production.     

Multi-electron storage of photoenergy using Cu2O–TiO2 thin film photocatalyst

UV–vis irradiation of thin films of TiO₂ (ITO/TiO₂) and Cu₂O/TiO₂ (ITO/Cu₂O/TiO₂) coated on conducting glasses generate H₂ from H₂O and once the illumination is ceased, the H₂ production was still noticeable under dark for ITO/Cu₂O/TiO₂ at a lesser production rate for up to 2 h. No such dark reactions were observed for ITO/TiO₂ or TiO₂-coated copper metal foil (Cu/TiO₂). It was noticed that the irradiation of ITO/Cu₂O/TiO₂ leads to formation of trapped electrons and this stored energy leads to generate H₂ from H₂O in the dark.     

Facile fabrication of mesoporous TiO2 electrodes for dye solar cells: chemical modification and repetitive coating

A chemical dispersing technique for preparing a coating paste of TiO₂ nanoparticles is disclosed to fabricate mesoporous electrodes for dye-sensitized TiO₂ solar cells. The suspension of TiO₂ (P-25) powder was stirred in aqueous nitric acid at 80°C, and then evaporated to dryness, giving the nitric acid-adsorbed P-25 powder. The coating paste was obtained by mixing the nitric acid-adsorbed P-25 with PEG (M_w 20,000) as a porosity-controlling agent and cellulosic polymer as a thickener. The mesoporous TiO₂ films were fabricated on conducting glasses by repetitive coating and calcined at 500°C (30 min). The TiO₂ film obtained by the five times repetitive coating (20 μm thickness) resulted in the 1.4 times higher energy conversion efficiency of the dye-sensitized solar cells than that of the one time coating TiO₂ film (V_oc=690 mV, J_sc=12.2 mA/cm², the fill FACTOR=0.71 and η=6.0%).     

Direct Z-scheme anatase/rutile bi-phase nanocomposite TiO2 nanofiber photocatalyst with enhanced photocatalytic H2-production activity

Design and preparation of direct Z-scheme anatase/rutile TiO₂ nanofiber photocatalyst to enhance photocatalytic H₂-production activity via water splitting is of great importance from both theoretical and practical viewpoints. Herein, we develop a facile method for preparing anatase and rutile bi-phase TiO₂ nanofibers with changing rutile content via a slow and rapid cooling of calcined electrospun TiO₂ nanofibers. The phase structure and composition, surface morphology, specific surface area, surface chemical composition and element chemical states of TiO₂ nanofibers were analyzed by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), nitrogen adsorption and X-ray photoelectron spectroscopy (XPS). By a rapid cooling of 500 °C-calcined electrospun TiO₂ precursor, anatase/rutile bi-phase TiO₂ nanofibers with a roughly equal weight ratio of 55 wt.% anatase and 45 wt.% rutile were prepared. The enhanced H₂ production performance was observed in the above obtained anatase/rutile composite TiO₂ nanofibers. A Z-scheme photocatalytic mechanism is first proposed to explain the enhanced photocatalytic H₂-production activity of anatase/rutile bi-phase TiO₂ nanofibers, which is different from the traditional heterojunction electron–hole separation mechanism. This report highlights the importance of phase structure and composition on optimizing photocatalytic activity of TiO₂-based material.     

Efficient photochemical hydrogen production under visible-light over artificial photosynthetic systems

Photosynthesis of green plants provides an effective blueprint for transform solar energy into useful hydrogen energy. Thereinto, their hierarchical structures are favorable to the light-harvesting. Meanwhile, the functional components (light-harvesting pigments) can absorb visible wavelengths of sunlight, and offer reaction center for the energy transform. Inspired by these, we contrive an artificial photosynthetic system for the high efficiency of H₂-production rate by introducing a similar functional structure (reticular hierarchical structure) and component (CdS/Pt–TiO₂). The CdS/Pt–TiO₂ with hierarchically reticular structure is prepared by transforming wings into TiO₂ via a sol–gel process, and depositing Pt and CdS nanoparticles onto the TiO₂ substrate by photoreduction and chemical bath deposition method, respectively. Contributing to the couple effect of reticular hierarchical structure and ternary hybrid composition, CdS/Pt–TiO₂ nanocomposites exhibit high visible-light photocatalytic H₂-production rate (12.7% apparent quantum efficiency obtained at 420 nm). This concept provides a new horizon to exploit solar energy for sustainable energy by imitating the photosynthesis process from structure and ingredients.     

Photoreduction of CO2 to fuels under sunlight using optical-fiber reactor

An optical-fiber reactor is employed to photocatalytically reduce CO₂ with H₂O to fuels under UVA artificial light and concentrated natural sunlight. The optical fiber is coated with gel-derived TiO₂–SiO₂ mixed oxide-based photocatalysts. Fe atom is found to insert into the TiO₂–SiO₂ lattice during sol–gel process, resulting in the full visible light absorption as well as the effect on product selectivity of the derived catalyst. Under UVA, ethylene is mainly produced on Cu–Fe/TiO₂ catalyst with the quantum yield of 0.0235%, whereas Cu–Fe/TiO₂–SiO₂ catalyst is observed to favor methane production with the quantum yield of 0.05%. Meanwhile, the overall energy efficiency is found to be much higher on Cu–Fe/TiO₂–SiO₂ (0.0182%) than on its Cu–Fe/TiO₂ counterpart (0.0159%). There is only methane evolved over both bare TiO₂–SiO₂ and Cu–Fe/TiO₂–SiO₂ catalysts under natural sunlight with the production rates of 0.177 and 0.279 μmol/g-cat h, respectively. For the former catalyst, the increase in light intensity is not found to compensate the inherent electron–hole recombination in the TiO₂–SiO₂–acac catalyst, whereas the superior photoactivity of Cu–Fe/TiO₂–SiO₂ catalyst under natural sunlight could be ascribed to its full absorption of visible light.     

Tri-layer antireflection coatings (SiO2/SiO2–TiO2/TiO2) for silicon solar cells using a sol–gel technique

Antireflection coatings (ARCs) have become one of the key issues for mass production of Si solar cells. They are generally performed by vacuum processes such as thermal evaporation, reactive sputtering, and plasma-enhanced chemical vapor deposition. In this work, a sol–gel method has been demonstrated to prepare the ARCs for the non-textured monocrystalline Si solar cells. The spin-coated TiO₂ single-layer, SiO₂/TiO₂ double-layer and SiO₂/SiO₂–TiO₂/TiO₂ triple-layer ARCs were deposited on the Si solar cells and they showed good uniformity in thickness. The measured average optical reflectance (400–1000 nm) was about 9.3, 6.2 and 3.2% for the single-layer, double-layer and triple-layer ARCs, respectively. Good correlation between theoretical and experimental data was obtained. Under a triple-layer ARC condition, a 39% improvement in the efficiency of the monocrystalline Si solar cell was achieved. These indicate that the sol–gel ARC process has high potential for low-cost solar cell fabrication.     

Direct synthesis of nanocrystalline titanium dioxide/carbon composite and its catalytic effect on NaAlH4 for hydrogen storage

Nanocrystalline titanium dioxide/carbon composite (TiO₂/C) was synthesized through a direct solution-phase carburization using tetrabutyl titanate (Ti(OBu)₄) and resol as precursors. The prepared TiO₂/C composite was mainly in the anatase structure with an average particle size under 20 nm, which was then introduced in NaAlH₄ as a catalyst through ball milling. The desorption curves show that both nanocrystalline TiO₂/C and TiO₂ can obviously improve the kinetics of NaAlH₄, while NaAlH₄ with 3 mol% TiO₂/C exhibits better cycling stability than NaAlH₄ with 3 mol%TiO₂. The hydrogen storage capacity of NaAlH₄ with TiO₂/C remains stable after 5th cycle, and about 94% of initial hydrogen is released, while the capacity of NaAlH₄ with TiO₂ decreases continuously during cycling, and only 88% of initial hydrogen is released after 10th cycle. Furthermore, NaAlH₄ with 3 mol%TiO₂/C exhibits good reversibility at relatively low hydrogen pressures, and it can reload 4.16 and 1.63wt% hydrogen at 50 and 30 bar hydrogen pressures, respectively.     

Synergistic effect of Cu2O/TiO2 heterostructure nanoparticle and its high H2 evolution activity

Cu₂O/TiO₂ nanoparticles were prepared by solvothermal method, which formed the heterostructure of Cu₂O/TiO₂. Due to the heterostructure, the H₂ evolution rate under simulated solar irradiation was increasingly promoted. Meanwhile a certain amount of Cu particles which were confirmed by Transmission Electro Microscopy (TEM) and X-Ray Photoelectron Spectroscopy (XPS), formed on the surface of Cu₂O/TiO₂, and the photoactivity was accordingly further enhanced. The stabilized activity was maintained after many times irradiation. It is interesting that after a few hours irradiation the amount of Cu particles on the surface kept unchanged in the presence of Cu₂O and TiO₂. The Cu particles that formed during hydrogen generation reaction play a key role in the further enhancement of the hydrogen production activity. In this study, it is the first time to study the details on the formation of the stable ternary structure under simulated solar irradiation and their synergistic effect on the photoactivity of the water splitting.     

The adsorption and dissociation of H2O on TiO2(110) and M/TiO2(110) (M = Pt,Au) surfaces–A computational investigation

The adsorption and dissociation of H₂O on clean TiO₂(110) and metal-deposited M/TiO₂(110) (M = Pt and Au) surfaces were studied by performing calculations of periodic density-functional theory. M/TiO₂(110) surfaces catalytically decompose H₂O with barriers (decreased by ca. 15–19 kcal/mol) much smaller than for their clean TiO₂(110) counterparts. The Au-deposited TiO₂ surface has the least energy barrier (ca. 3.5 kcal/mol less than the Pt analogue), explicable with a Bader charge analysis.     

CO2 and H2O reduction by solar thermochemical looping using SnO2/SnO redox reactions: Thermogravimetric analysis

The thermochemical dissociation of CO₂ and H₂O from reactive SnO nanopowders is studied via thermogravimetry analysis. SnO is first produced by solar thermal dissociation of SnO₂ using concentrated solar radiation as the high-temperature energy source. The process targets the production of CO and H₂ in separate reactions using SnO as the oxygen carrier and the syngas can be further processed to various synthetic liquid fuels. The global process thus converts and upgrades H₂O and captured CO₂ feedstock into solar chemical fuels from high-temperature solar heat only, since the intermediate oxide is not consumed but recycled in the overall process. The objective of the study was the kinetic characterization of the H₂O and CO₂ reduction reactions using reactive SnO nanopowders synthesized in a high-temperature solar chemical reactor. SnO conversion up to 88% was measured during H₂O reduction at 973 K and an activation energy of 51 ± 7 kJ/mol was identified in the temperature range of 798-923 K. Regarding CO₂ reduction, a higher temperature was required to reach similar SnO conversion (88% at 1073 K) and the activation energy was found to be 88 ± 7 kJ/mol in the range of 973-1173 K with a CO₂ reaction order of 0.96. The SnO conversion and the reaction rate were improved when increasing the temperature or the reacting gas mole fraction. Using active SnO nanopowders thus allowed for efficient and rapid fuel production kinetics from H₂O and CO₂.     

Photocatalytic activity of N, S co-doped and N-doped commercial anatase TiO2 powders towards phenol oxidation and E. coli inactivation under simulated solar light irradiation

Nitrogen and sulfur co-doped and N-doped TiO₂ anatase TKP 102 (Tayca) were prepared by manual grinding with thiourea and urea, respectively, and annealing at 400 °C. Both materials showed visible-light absorption as measured by Diffuse Reflectance Spectroscopy (DRS). Interstitial N-doping, anionic and cationic S-doping was found when the TiO₂ was doped with thiourea while TiO₂ doped with urea showed only the presence of interstitial N-doping as measured by X-ray Photo-electron Spectroscopy (XPS). The N content on the surface of N-doped TKP 102 photocatalyst was 2.85 at.% and higher than the N content in the N, S co-doped TiO₂ photocatalyst (0.6 at.%).The photocatalytic activity of the doped catalysts was tested using phenol and Escherichia coli as chemical and biological targets, respectively, using N, S co-doped, N-doped TiO₂, undoped Degussa P-25 and undoped TKP 102 powders under simulated solar light. It was found that undoped Degussa P-25 was the photocatalyst with the highest photocatalytic activity towards phenol oxidation and E. coli inactivation. N, S co-doped powders showed almost the same photocatalytic activity as undoped TKP 102 while N-doped TKP 102 was the less active photocatalyst probably due the N impurities on the TiO₂ acting as recombination centers.     

Synthesis of reduced graphene oxide–TiO2 nanoparticle composite systems and its application in hydrogen production

The utilization of solar energy for the conversion of water to hydrogen and oxygen has been considered to be an efficient strategy to solve crisis of energy and environment. Here, we report the synthesis of reduced graphene oxide–TiO₂ nanoparticle composite system through the photocatalytic reduction of graphite oxide using TiO₂ nanoparticles. Photoelectrochemical characterizations and hydrogen evolution measurements of these nanocomposites reveal that the presence of graphene enhances the photocurrent density and hydrogen generation rate. The optimum photocurrent density and hydrogen generation rate has been found to be 3.4 mA cm⁻² and 127.5 μmole cm⁻²h⁻¹ in 0.5 M Na₂SO₄ electrolyte solution under 1.5AM solar irradiance of white light with illumination intensity of 100 mW cm⁻². In graphene–TiO₂ nanocomposite, photogenerated electrons in TiO₂ are scavenged by graphene sheets and percolate to counter electrode to reduce H⁺ to molecular hydrogen thus increasing the performance of water-splitting reaction.     

Photocatalytic splitting of seawater and degradation of methylene blue on CuO/nano TiO2

The main objective of this study was to prepare effective photocatalysts for splitting of seawater for solar fuel – H₂ and degradation of seawater organic pollutants such as dyes. To enhance photocatalytic activities, CuO is supported on nano TiO₂ (CuO/nano TiO₂). By X-ray absorption near edge structure (XANES) spectroscopy, CuO clusters are found on nano TiO₂. The 2.5% CuO/nano TiO₂ has greater activities in photocatalytic splitting of water and seawater than nano TiO₂ by 9.9 and 7.8 times, respectively. Interestingly, the 2.5% CuO/nano TiO₂ is also very active for photocatalytic splitting of water and seawater contaminated with dyes such as methylene blue (MB) (10 ppm). Under a 5-h irradiation of the UV–Vis light, about 99% of MB is degraded while 3.1 μmol/h g cat of H₂ are generated from seawater in the photocatalysis process.