Hydrogen production upon UV-light irradiation of Cu/TiO2 photocatalyst in the presence of alkanol-amines

Photocatalytic hydrogen production from alkanol-amines as sacrificial agents by using Cu-modified TiO₂–P25 prepared via in situ photodeposition of cupric ions under UV-A light irradiation was investigated. A direct comparison among different sacrificial agents (monoethanolamine, diethanolamine, and triethanolamine) was preliminarily performed. Diethanolamine was selected for further investigation, due to its higher hydrogen production rate with respect to other alkanol-amines. Effect of pH, starting concentration of sacrificial agent, and catalyst/co-catalyst loads were studied. Solution pH exerts major impact on the photoefficiency for hydrogen generation: reaction mechanisms at different pH values were extensively examined. For the first time, a validated kinetic model estimated the unknown rate constants of (i) reaction between diethanolamine and photogenerated holes, (ii) proton reduction, and (iii) diethanolamine adsorption on the photocatalyst surface.     

CuO@NiO core-shell nanoparticles decorated anatase TiO2 nanospheres for enhanced photocatalytic hydrogen production

Core-shell structured co-catalyst has been created much attention in photocatalytic hydrogen production due to their efficient electron-hole pair separation, suppression of surface back reaction and long term stability. Here, we report the preparation of CuO@NiO hierarchical nanostructures as a co-catalyst deposited on TiO₂ nanospheres for enhanced photocatalytic hydrogen generation. The formation of ultrathin NiO shell over the CuO core was confirmed by TEM analysis. Fabricated core-shell nanostructured CuO@NiO over TiO₂ nanospheres was studied for hydrogen evolution under the direct solar light and it showed a high rate of H₂ production of 26.1 mmol. h⁻¹. g⁻¹_cat. It was scrutinized that the rate of hydrogen production was improved with shell thickness and co-catalyst loading. Systematic investigation on CuO@NiO co-catalyst loading, pH of the medium and glycerol concentration for augmented H₂ production. The recorded rate of hydrogen production is almost six folds greater than that of pristine TiO₂. In the view of largescale synthesis for alternative energy storage applications, the composited photocatalyst was made of by simple mixing method, which could be scaled up without any loss in photocatalytic activity. Further, the stability test of photocatalyst for continuous use found that 82% of initial photocatalytic activity is retained even after three days.     

Kinetic study of the effects of pH on the photocatalytic hydrogen production from alcohols

Solution pH is an important parameter in photocatalytic reactions that substantially affects the process by changing photocatalyst agglomeration and substrate adsorption on photocatalyst surface. In this work, a kinetic study was performed on photocatalytic hydrogen production from alcohols and an intrinsic kinetic model was developed to predict the rate of hydrogen production from different alcohols as a function of pH. Glycerol, ethanol, and methanol were selected as representative substrates and tested in a pH range of 2–12. The very good agreement between model predictions and experimental data was confirmed by statistical analyses (R², R²_adj, RMS, AAD, and MAE). The results revealed that for all substrates investigated, the maximum hydrogen rate was obtained at a pH~8. A local minimum for hydrogen production was observed around pHzpc, as a result of catalyst agglomeration. The results of this study can be very useful in future investigations of the effects of pH on other aqueous phase photocatalytic processes.     

Experimental design as a tool to study the reaction parameters in hydrogen production from photoinduced reforming of glycerol over CdS photocatalyst

The aim of this study was to set the reaction conditions of the photoinduced reforming of glycerol aqueous solution over Pt/hex-CdS under visible light irradiation for enhancement of hydrogen production by using a fractional factorial experimental design followed by a Box–Behnken design. The parameters assessed were irradiation time, mass of photocatalyst, concentration of glycerol, pH and electrolyte concentration (NaCl). The preliminary two-level fractional factorial design (2⁵⁻¹) showed that all of the investigated factors have significant effect in hydrogen production, being pH the most important parameter. The three factors Box–Behnken design showed maximum response for hydrogen production in pH 4.0, 55% glycerol and 1.5 mol L⁻¹ NaCl. The amount of hydrogen obtained under these conditions was 270% higher than our previous result, using the same photocatalyst and electron donor. In the ideal pH, >CdSH₂⁺and >CdOH species are predominant before irradiation, indicating that such species play an important role in the primary steps of the photoelectrochemical mechanism, which served as the basis for proposing a mechanism for hydrogen generation as well as glycerol photooxidation. Based on the surface response [NaCl] × [glycerol], a solution with salinity equivalent to approximately the natural seawater was tested and the result for hydrogen production was comparable to the best condition; besides, under this condition, the solubility of CdS in aqueous solution is reduced.     

Highly efficient photocatalytic hydrogen evolution by using Rh as co-catalyst in the Cu/TiO2 system

Cu/TiO₂ was modified by adding Rh as co-catalyst and used as a highly efficient photocatalyst for the hydrogen evolution reaction. A low amount of Rh was loaded onto Cu/TiO₂ by the deposition-precipitation with urea (DPU) method to observe the effect on the hydrogen production displayed by different samples. The Rh–Cu/TiO₂ oxide structure exhibited a remarkably high photocatalytic hydrogen evolution performance, which was about twofold higher than that of the Cu/TiO₂ monometallic photocatalyst. This outstanding performance was due to the efficient charge carrier transfer as well as to the delayed electron-hole recombination rate caused by the addition of Rh. The influence of the different parameters of the photocatalyst synthesis and reaction conditions on the photocatalytic activity was investigated in detail. Hydrogen evolution was studied using methanol, ethanol, 2-propanol and butanol as scavengers with an alcohol:water ratio of 20:80. The methanol-water system, which showed the highest hydrogen production, was studied under 254, 365 and 450 nm irradiation; Rh–Cu/TiO₂ showed high photocatalytic activity with H₂ production rates of 9260, 5500, and 1940 μmol h^?1 g^?1, respectively. The Cu–Rh/TiO₂ photocatalyst was active under visible light irritation due to its strong light absorption in the visible region, low band gap value and ability to reduce the electron (e^?) and hole (h⁺) recombination.     

Enhancing hydrogen evolution of water splitting under solar spectra using Au/TiO2 heterojunction photocatalysts

An effective improvement of hydrogen evolution from water splitting under solar light irradiation was investigated using quantum dots (QDs) compounds loaded onto a Au/TiO₂ photocatalyst. First, Au/TiO₂ was prepared by the deposition-precipitation method, and then sulfide QDs were loaded onto the as-prepared Au/TiO₂ by a hydrothermal method. QDs were loaded onto Au/TiO₂ to enhance the energy capture of visible light and near-infrared light of the solar spectrum. The results indicated that the as-prepared heterojunction photocatalysts absorbed the energy from the range of ultraviolet light to the near-infrared light region and effectively reduced the electron-hole pair recombination during the photocatalytic reaction. Using a hydrothermal temperature of 120 °C, the as-prepared (ZnS–PbS)/Au/TiO₂ photocatalyst had a PbS QDs particle size of 5 nm, exhibited an energy gap of 0.92 eV, and demonstrated the best hydrogen production rate. Additionally, after adding 20 wt % methanol as a sacrificial reagent to photocatalyze for 5 h, the hydrogen production rate reached 5011 μmol g⁻¹ h⁻¹.     

Photocatalytic hydrogen production from aqueous methanol solution using titanium dioxide with the aid of simultaneous metal deposition

The photocatalytic hydrogen generation from aqueous methanol solution using TiO₂ photocatalyst was investigated with the aid of simultaneous metal deposition. The photocatalytic hydrogen evolution with pure TiO₂ was very small. The simultaneous deposition for various metals was therefore evaluated. As a result, the additions of Au and Cu ions were effective for the improvement of photocatalytic hydrogen production. Methanol concentration and metal ion concentration were optimized for the system. The optimal methanol concentrations were 90 and 80 vol% in the case of addition of Au and Cu ions, respectively. Under the optimal conditions, the photocatalytic hydrogen production using TiO₂ photocatalyst with the aid of simultaneous Cu and Au deposition were approximately 25 and 120 times larger than those obtained with bare TiO₂.     

A columnar regular-porous stainless steel reaction support with high superficial area for hydrogen production

To improve hydrogen production (HP) performance of regular-porous structure (RPS), a columnar RPS with small specific surface area and high superficial area is developed. A numerical simulation model of regular-porous stainless steel structure (RPSSS) is established. Subsequently, heat transfer performance, pressure loss, temperature, methanol concentration, H₂ concentration distributions and HP performance of the columnar RPSSS with small specific surface area and high superficial area and the body-centered cubic RPSSS with high specific surface area and small superficial area are compared. Then, temperature, methanol concentration, H₂ concentration distributions and HP performance of axial and longitudinal size-enlarged columnar RPSSSs are studied. The results show that compared to the body-centered cubic RPSSS, the columnar RPSSS has higher methanol conversion, larger H₂ flow rate and higher CO selectivity. Especially in the condition of 300 °C wall temperature and 12 mL/h methanol-water mixture injection rate (MWMIR), the methanol conversion, H₂ flow rate and CO selectivity of the columnar RPSSS are increased by 12.3%, 9.24% and 30%, respectively, indicating that the superficial area of RPSSS is more important for its HP performance compared to its specific surface area. Compared to the longitudinal size-enlarged columnar RPSSS, the axial size-enlarged columnar RPSSS has higher methanol conversion, larger H₂ flow rate and higher CO selectivity. This research work provides a new method for the optimization of hydrogen production reaction support (HPRS).     

Efficient hydrogen evolution by liquid phase plasma irradiation over Sn doped ZnO/CNTs photocatalyst

In this study, the liquid phase plasma (LPP) was irradiated over pure zinc oxide (ZnO), strontium (Sn) doped ZnO, and Sn doped ZnO/CNTs photocatalysts for hydrogen evolution from pure water and from aqueous solution of water-methanol. The possible relationship between hydrogen evolution and optical emissions from LPP for activation of ZnO based photocatalysts was revealed. The role of carbon nanotubes (CNTs) as a support material for improved photocatalytic hydrogen evolution was also investigated in this study. The photocatalytic hydrogen evolution from water mixed methanol under LPP irradiation was compared with pure water splitting. The photolysis produced negligible amount of hydrogen due to minimal photodecomposition of water molecules under LPP irradiation. The plasma born reactive species also played crucial role in photolysis. However, the hydrogen evolution rate increased significantly in the presence of ZnO photocatalyst. Further improvement in hydrogen evolution rate was noticed on Sn doping of ZnO and compositing with CNTs. The highest hydrogen evolution rate of 11.46 mmh⁻¹g⁻¹ from water mixed methanol was achieved with Sn doped ZnO/CNTs photocatalyst. This hydrogen evolution rate from water-methanol solution was 9 times higher than from the splitting of pure water. This hydrogen evolution rate is attributed to excessive production of hydroxyl radicals, red shift in optical band gap of Sn doped ZnO/CNTs photocatalyst, slow electron-hole recombination and fast decomposition of methanol as sacrificial reagent.     

The design of a hierarchical photocatalyst inspired by natural forest and its usage on hydrogen generation

A novel photocatalyst was designed from the inspiration of natural forest's high efficient on light harvesting and energy conversion. This novel “forest-like” photocatalyst was successfully synthesized by a facile continuously-conducted three steps methods: electrospinning TiO₂ nanofiber acts as the trunks, hydrothermal growth ZnO nanorods on the surface of TiO₂ nanofiber acts as the branches, while photodeposition of Cu nanoparticles on the surface of TiO₂ nanofiber and ZnO nanorods act as the leaves. This novel photocatalyst demonstrated higher photocatalytic hydrogen generation rate than most of semiconductor catalysts and many newly developed catalysts such as Pt/TiO₂ catalyst and artificial leaves Pt/N–TiO₂ catalyst in a water/methanol sacrificial reagent system under the light irradiation as a result of its enhanced light absorption ability, enlarged specific surface area promoting mass transfer and providing more reaction sites and its potential on anti-recombination of electrons and holes. Meanwhile, it is interesting to note that the photocatalytic hydrogen generation activity has a liner relationship with the hierarchy of materials, which means higher hierarchy materials display higher photocatalytic hydrogen generation activity. It is reasonable to believe that this natural mimic photocatalyst without noble metals will benefit the energy generation and novel materials development.     

TiO2 nanosheets loaded with Cu: A low-cost efficient photocatalytic system for hydrogen evolution from water

Rutile TiO₂ nanosheets were prepared by a simple solvothermal process, and Cu was loaded on the surface of TiO₂ nanosheets using the in situ photo-deposition method. Meanwhile, photocatalytic H₂ evolution from water over the as-prepared TiO₂ nanosheets loaded with Cu was explored using methanol as a sacrificial reagent. The results indicate that the TiO₂ nanosheets loaded with Cu is an efficient photocatalyst under UV irradiation. During the first 5 h, a rate of H₂ evolution of approximately 22.1 mmol g⁻¹ h⁻¹ was achieved under optimal conditions. Furthermore, for practical purposes, the photocatalytic hydrogen evolution was studied as a function of content of Cu, pH of solution, concentration of methanol and dosage of photocatalyst, respectively. At last, the photocatalytic mechanism was preliminarily discussed.     

Photoelectrocatalytic reduction of CO2 to methanol over CuFe2O4@PANI photocathode

The present study was aimed to convert CO₂ into methanol which not only addresses the potential solution for controlling the CO₂ concentration level in the atmosphere but also offers an alternative approach for the production of renewable energy source. In this perspective, a hybrid photocatalyst, PANI@CuFe₂O₄ was synthesized, characterized and used as a photocathode for photoelectrocatalytic (PEC) reduction of CO₂ to methanol in aqueous medium at an applied potential of ?0.4 V vs NHE under visible light irradiation. The combination of PANI with CuFe₂O₄ greatly increased the PEC CO₂ reduction to methanol owing to enhance the CO₂ chemisorption capacity by the photocathode surface and at the same time facilitated the separation of photogenerated electron-hole (e^?/h⁺) pairs. The incident photon to current efficiency (IPCE) and quantum efficiency (QE) for methanol formation in PEC CO₂ reduction could be achieved as 7.1 and 24.0% respectively. The rate of formation of methanol in PEC CO₂ reduction was found as 49.3 μmol g^?1h^?1 with 73% Faradaic efficiency. Compared to photocatalytic reaction, the PEC results demonstrated that the applied potential could effectively separate the photogenerated e^?/h⁺ pairs and therefore, enhanced the PEC CO₂ reduction activity of the hybrid photocatalyst.     

Improving hydrogen production via water splitting over Pt/TiO2/activated carbon nanocomposite

Mesoporous TiO₂/AC, Pt/TiO₂ and Pt/TiO₂/AC (AC = activated carbon) nanocomposites were synthesized by functionalizing the activated carbon using acid treatment and sol–gel method. Photochemical deposition method was used for Pt loading. The nano-photocatalysts were characterized using XRD, SEM, DRS, BET, FTIR, XPS, CHN and ICP methods. The hydrogen production, under UV light irradiation in an aqueous suspension containing methanol has been studied. The effect of Pt, methanol and activated carbon were investigated. The results show that the activated carbon and Pt together improve the hydrogen production via water splitting. Also methanol acts as a good hole scavenger. Mesoporous Pt/TiO₂/AC nanocomposite is the most efficient photocatalyst for hydrogen production compared to TiO₂/AC, Pt/TiO₂ and the commercial photocatalyst P25 under the same photoreaction conditions. Using Pt/TiO₂/AC, the rate of hydrogen production is 7490 μmol (h g catal.)⁻¹ that is about 75 times higher than that of the P25 photocatalyst.     

Hydrogen production by cracking of ammonium hydroxide using liquid-phase plasma on the modified TiO2 photocatalysts

Ammonia is a promising material as a direct source of green hydrogen production. This paper reports a method for mass production of hydrogen from liquid NH₃(NH₄OH) through a photocatalytic decomposition reaction using liquid plasma. In this reaction, the highest hydrogen production rate was observed in the TiO₂ photocatalyst doped with N and metal ions as a photocatalyst sensitive to visible light with a low bandgap. At this time, the hydrogen production rate was obtained as about 142 L/g?h. This is due to the high photoactivity of the visible light-sensitive photocatalyst in liquid plasma emitting strong visible light and ultraviolet light. The H₂ production rate obtained from the decomposition of liquid NH₃ by plasma discharge to the catalyst was higher than the H₂ production rate obtained from the NH₃ electrolysis process.     

Photocatalytic H2 production from acetic acid solution over CuO/SnO2 nanocomposites under UV irradiation

The CuO/SnO₂ composites have been prepared by the simple co-precipitation method and further characterized by the XRD, FESEM and Raman spectroscopy. The photocatalytic H₂ production from acetic acid (HAc) solution over CuO/SnO₂ photocatalyst has been investigated at room temperature under UV irradiation. Effects of CuO loading, photocatalyst concentration, acetic acid concentration and pH on H₂ production have been systematically studied. Compared with pure SnO₂, the 33.3 mol%CuO/SnO₂ composite exhibited approximately twentyfold enhancement of H₂ production. The H₂ yield is about 0.66 mol-H₂/mol-HAc obtained under irradiation for prolonged time. The Langmuir-type model is applied to study the dependence of hydrogen production rate on HAc concentration. A possible mechanism for photocatalytic degradation of acetic acid over CuO/SnO₂ photocatalyst is proposed as well. Our results provide a method for pollutants removal with simultaneous hydrogen generation. Due to simple preparation, high H₂ production activity and low cost, the CuO/SnO₂ photocatalyst will find wide application in the coming future of hydrogen economy.     

Photocatalytic H2 production from water splitting under visible light irradiation using Eosin Y-sensitized mesoporous-assembled Pt/TiO2 nanocrystal photocatalyst

Sensitized photocatalytic production of hydrogen from water splitting is investigated under visible light irradiation over mesoporous-assembled titanium dioxide (TiO₂) nanocrystal photocatalysts, without and with Pt loading. The photocatalysts are synthesized by a sol–gel process with the aid of a structure-directing surfactant and are characterized by N₂ adsorption–desorption analysis, X-ray diffraction, UV–vis spectroscopy, scanning electron microscopy, transmission electron microscopy and energy-dispersive X-ray analysis. The dependence of hydrogen production on the type of TiO₂ photocatalyst (synthesized mesoporous-assembled and commercial non-mesoporous-assembled TiO₂ without and with Pt loading), the calcination temperature of the synthesized photocatalyst, the sensitizer (Eosin Y) concentration, the electron donor (diethanolamine) concentration, the photocatalyst dosage and the initial solution pH is systematically studied. The results show that in the presence of the Eosin Y sensitizer, the Pt-loaded mesoporous-assembled TiO₂ synthesized by a single-step sol–gel process and calcined at 500 °C exhibits the highest photocatalytic activity for hydrogen production from a 30 vol.% diethanolamine aqueous solution with dissolved 2 mM Eosin Y. Moreover, the optimum photocatalyst dosage and initial solution pH for the maximum photocatalytic activity for hydrogen production are 3.33 g dm⁻³ and 11.5, respectively.     

Correlation of hydrogen generation and optical emission properties of plasma in water photolysis on perovskite photocatalysts

Photocatalytic decomposition of organic materials-contained aqueous solution is assessed using a plasma discharged into the liquid directly. The correlation of H₂ generation and optical emission spectroscopy is discussed in terms of photocatalytic H₂ production using plasma and photocatalysts. Variations of the active species are evaluated according to the conditions of the plasma in the liquid phase. The optical emission spectra vary according to the plasma discharging conditions in the liquid phase. The intensities of the OH· peaks at 309 nm increase with the addition of ethanol or acetaldehyde in water. The highest intensities and rate of H₂ evolution are observed at a 10% acetaldehyde concentration in the aqueous solution. The rates of H₂ evolution in the ethanol or acetaldehyde solution correspond to the concentration of OH· in the solution. The photocatalytic reaction using liquid plasma generates hydrogen at the same time as the decomposition of the organic chemicals. The rate of hydrogen evolution in aqueous solutions containing the organic chemicals is higher than that in pure water. This is because hydrogen is further generated due to hydrogen generation by photolysis of the organic chemicals. CaTiO₃ perovskite photocatalyst shows better photocatalytic activity than TiO₂. Ni loading on the photocatalyst lead to an increase in H₂ production.     

Porous copper fiber sintered felts with surface microchannels for methanol steam reforming microreactor for hydrogen production

In this study, a laser micro-milling technique was introduced into the fabrication process of surface microchannels with different geometries and dimensions on the porous copper fiber sintered felts (PCFSFs). The PCFSFs with surface microchannels as catalyst supports were then used to construct a new type of laminated methanol steam reforming microreactor for hydrogen production. The microstructure morphology, pressure drop, velocity and permeability of PCFSF with surface microchannels were studied. The effect of surface microchannel shape (rectangular, stepped, and polyline) and catalyst loading amount on the reaction performance of methanol steam reforming microreactor for hydrogen production was further investigated. Our results show that the PCFSF with rectangular microchannels demonstrated a lower pressure drop, higher average velocity and higher permeability compared to the stepped and polyline microchannel. Furthermore, the PCFSF with rectangular microchannels also exhibited the highest methanol conversion and H₂ flow rate. The best reaction performance of methanol steam reforming microreactor for hydrogen production was obtained using PCFSF with rectangular microchannels when 0.5 g catalyst was loaded.     

Photocatalytic hydrogen evolution with simultaneous degradation of organics over (CuIn)0.2Zn1.6S2 solid solution

Using various organics as electron donor, (CuIn)_0.2Zn_1.6S₂ microsphere solid solution prepared via hydrothermal method as photocatalyst, hydrogen production by anaerobic photocatalytic reforming organics were researched. The photocatalytic hydrogen production activity was notably enhanced in the presence of the organic electron donors. Formic acid was found to be the most efficient sacrificial agent among methanol, glucose, triethanolamine and formic acid. The effects of initial formic acid concentration on hydrogen generation were investigated. When the initial formic acid concentration was 10 vol%, the photocatalytic activity reached the highest. The average activity in initial 10 h can amount to 144 μmol h⁻¹. The possible mechanism of photocatalytic reaction for hydrogen production with simultaneous formic acid degradation was discussed preliminary.     

Hydrogen production from cylindrical methanol steam reforming microreactor with porous Cu-Al fiber sintered felt

In this study, the porous Cu-Al fiber sintered felt (PCAFSF) was fabricated by low temperature solid-phase sintering method. The laminated PCAFSF as the catalyst support was used for cylindrical methanol steam reforming microreactor for hydrogen production. The two-layer impregnation method was employed to coat the Cu/Zn/Al/Zr catalyst on the PCAFSF. The material composition, specific surface area and catalyst loading of PCAFSF were also measured. The effect of the fiber material, surface morphology and porosity on the reaction performance of methanol steam reforming microreactor for hydrogen production was further investigated. Our results show that the PCAFSF demonstrated much higher methanol conversion and H₂ flow rate compared to the porous Cu fiber sintered felt (PCFSF) and porous Al fiber sintered felt (PAFSF) having the same porosity. Furthermore, the rough PCAFSF showed much higher methanol conversion and H₂ flow rate compared to the smooth PCAFSF. In case of the PCAFSF, the methanol conversion and H₂ flow rate were increased with the decrease of Cu fiber weight and the increase of Al fiber weight. The best reaction performance of microreactor for hydrogen production was obtained using the three layer PCAFSFs with 80% porosity and 1.12 g Cu fiber/1.02 g Al fiber.