Photocatalytic hydrogen production over CuO and TiO2 nanoparticles mixture

Cheap and efficient photocatalysts were fabricated by simply mixing TiO₂ nanoparticles (NPs) and CuO NPs. The two NPs combined with each other to form TiO₂/CuO mixture in an aqueous solution due to the opposite surface charge. The TiO₂/CuO mixture exhibited photocatalytic hydrogen production rate of up to 8.23 mmol h⁻¹ g⁻¹ under Xe lamp irradiation when the weight ratio of P25 to CuO was optimized to 10. Although the conduction band edge position of CuO NPs is more positive than normal hydrogen electrode, the TiO₂/CuO mixture exhibited good photocatalytic hydrogen production performance because of the inter-particle charge transfer between the two NPs. The detailed mechanism of the photocatalytic hydrogen production is discussed. This mixing method does not require a complicated chemical process and allows mass production of the photocatalysts.     

Development of durable copper catalyst for hydrogen production by high temperature methanol steam reforming

Highly durable catalyst for high temperature methanol steam reforming is required for a compact hydrogen processor. Deactivation of a coprecipitated Cu/ZnO/ZrO₂ catalyst modified with In₂O₃ is very gradual even in the high temperature methanol steam reforming mainly at 500 °C, but the initial activity is considerably low. Addition of Y₂O₃ to Cu/ZnO/ZrO₂/In₂O₃ increases its initial activity due to the higher Cu surface amount, while the activity comes gradually close to that for the catalyst without Y₂O₃ during the reaction. Coprecipitation of Cu/ZnO/ZrO₂/Y₂O₃/In₂O₃ on a zirconia support triply increases the overall activity by keeping the durability while the amount of the coprecipitated portion is a half of that without the support. On the composite catalyst, sintering of Cu particles is suppressed. The surface Cu amount is similar to that without the support, but the Cu surface activity is much higher probably because of the small Cu particle size.     

Thermal behavior and hydrogen production of methanol steam reforming and autothermal reforming with spiral preheating

The present study aims to investigate the thermal behavior and hydrogen production characteristics from methanol steam reforming (MSR) and autothermal reforming (ATR) under the effects of a Cu-Zn-based catalyst and spiral preheating. Two different reaction temperatures of 250 and 300 °C are taken into account. Meanwhile, the O/C ratio (i.e. the molar ratio between O₂ and methanol) and S/C ratio (i.e. the molar ratio between steam and methanol) are controlled in the ranges of 0-0.5 and 1-2, respectively. The condition of O/C = 0 represents the reaction of MSR. By monitoring the supplied power into the reactor with a fixed gas hourly space velocity (GHSV) of 72,000 h⁻¹, the experimental results indicate that an exothermic reaction from ATR can be attained once the O/C ratio is as high as 0.125. Increasing O/C ratio causes more heat released from the reaction, this results in the decrease in the frequency of supplied power, especially at O/C = 0.5. It is noted that the concentration of CO in the product gas is quite low compared to that of CO₂. An increase in O/C ratio abates the concentration of H₂ from the consumption of per mol methanol; however, the H₂ yield in terms of thermodynamic analysis is increased. On account of the utilization of spiral preheating on the reactants, within the investigated operating conditions the methanol conversion and hydrogen yield were always higher than 95 and 90%, respectively. A comparison suggests that the methanol conversion from ATR of methanol with spiral preheating is superior to those of other studies.     

Photocatalytic hydrogen production from aqueous methanol solution with CuO/Al2O3/TiO2 nanocomposite

The photocatalytic hydrogen production from aqueous methanol solution was investigated with ZnO/TiO₂, SnO/TiO₂, CuO/TiO₂, Al₂O₃/TiO₂ and CuO/Al₂O₃/TiO₂ nanocomposites. A mechanical mixing method, followed by the solid-state reaction at elevated temperature, was used for the preparation of nanocomposite photocatalyst. Among these nanocomposite photocatalysts, the maximal photocatalytic hydrogen production was observed with CuO/Al₂O₃/TiO₂ nanocomposites. A variety of components of CuO/Al₂O₃/TiO₂ photocatalysts were tested for the enhancement of H₂ formation. The optimal component was 0.2 wt% CuO/0.3 wt% Al₂O₃/TiO₂. The activity exhibited approximately tenfold enhancement at the optimum loading, compared with that with pure P-25 TiO₂. Nano-sized TiO₂ photocatalytic hydrogen technology has great potential for low-cost, environmentally friendly solar-hydrogen production to support the future hydrogen economy.     

Inhibitory effect of chloroform on fermentative hydrogen and methane production from lipid-extracted microalgae

To improve the sustainability of microalgae as a bioenergy feedstock, lipid-extracted microalgae (LEM) are often further treated by anaerobic digestion (AD). However, the residual chloroform used for extracting lipids as a solvent could inhibit this process, an aspect that has not been studied to date. In this study, the inhibitory effect of chloroform on H₂ and CH₄ production was investigated by performing batch tests. To prepare the feedstock, Chlorella vulgaris was ultrasonicated and the supernatant was discarded after centrifugation. In case of H₂ production, it was found that the H₂ yield fell to almost half that of the control (15.6 mL H₂/g COD_added) at 100 mg CHCl₃/L. The reason for the decrease of the H₂ yield with the increase of chloroform level was due to the change of metabolites from acetate and butyrate to lactate via a non-hydrogenic reaction. In comparison with H₂ production, a much more severe inhibitory effect of chloroform on CH₄ production was observed. The inhibitor concentration (IC_{30, 60, and 90}) on H₂ production was 138, 319, and 622 mg CHCl₃/L, respectively, while concentrations of 15, 37, and 86 mg CHCl₃/L were obtained on CH₄ production. When the chloroform concentration was ≥25 mg/L on CH₄ production, more than 2 g COD/L of organic acids remained, resulting in a decrease of CH₄ yield. These findings indicate that the residual chloroform in LEM should be seriously considered to prevent possible microbial inhibition when designing a process for additional energy recovery from microalgae via AD.     

High photocatalytic hydrogen production over the band gap-tuned urchin-like Bi2S3-loaded TiO2 composites system

A new system using Bi₂S₃-loaded TiO₂ photocatalysts (Bi₂S₃/TiO₂) was developed to enhance the production of hydrogen. The Bi₂S₃ (5, 10, 15 wt%) particles in an urchin-like morphology with a length of about 2∼3 μm and a diameter of 15–20 nm, which can absorb all wavelengths in UV–visible radiation, were prepared by solvothermal method and loaded onto nano-sized TiO₂ (10∼15 nm) for photocatalysis on hydrogen production. The evolution of H₂ from methanol/water (1:1) photo splitting over the Bi₂S₃/TiO₂ composite in the liquid system was enhanced, compared with that over pure TiO₂ and Bi₂S₃. In particular, 14.2 ml of H₂ gas was produced after 12 h when 0.5 g of a 10 wt% Bi₂S₃/TiO₂ composite was used. On the basis of cyclic voltammetry (CV) results, the high photoactivity was attributed to the increase of band gap in the Bi₂S₃/TiO₂ composite, due to the decreased recombination between the excited electrons and holes.     

Simultaneous utilization of two different membranes for intensification of ultrapure hydrogen production from recuperative coupling autothermal multitubular reactor

The potential of simultaneous hydrogen production and in situ water removal in a thermally coupled multitubular two-membrane reactor (TCTMR) were studied numerically. Methanol synthesis is carried out in exothermic side with H-SOD membrane and supplies the necessary heat for the endothermic side. Dehydrogenation of cyclohexane is carried out in endothermic side with hydrogen-permselective Pd/Ag membrane wall. Therefore, the proposed reactor consists of two membranes, one for separation of pure hydrogen from endothermic side and another one for separation of water from exothermic side. The motivation for in situ H₂O removal during methanol synthesis by using H-SOD membranes is to displace the water-gas shift equilibrium to enhance conversion of CO₂ to improve methanol productivity. A steady-state heterogeneous model is developed to analyze the operation of the coupled methanol synthesis. The proposed model has been used to compare the performance of a TCTMR with conventional reactor (CR) and thermally coupled membrane reactor (TCMR) at identical process conditions. This comparison shows that TCTMR in addition to possessing advantages of a TCMR has a more favorable profile of temperature and increased productivity compared with other reactors. Furthermore, lower water production rate in TCTMR reduces catalyst re-crystallization.     

Low voltage H2O electrolysis for enhanced hydrogen production

In this study, we report the ability to split H₂O into hydrogen at a reduced voltage by the influence of sulfur dioxide (SO₂) and anode tolerance materials. This will improve the energy consumption for the production of hydrogen. Hydrogen is produced at the cathode while the anode electrode is bathed in sulfur dioxide and water to form sulfuric acid by the application of potential in the form of electrical energy. In the presence of SO₂, the theoretical equilibrium voltage requirement is 0.19 V, thereby reducing the thermochemical free energy to less than one-sixth of its initial value, that is, from 56 to 9.18 kcal/mole. By using SO₂ to scavenge the anode we have in practice reduced the equilibrium voltage to 0.6 V. Based on different electrode configurations, ruthenium oxide (RuO₂) electrocatalyst deposited on silicon (Si) electrode exhibited superior performance for the low voltage H₂O electrolysis.     

Photocatalytic hydrogen production in the water/methanol system using Pt/RE:NaTaO3 (RE = Y,La, Ce,Yb) catalysts

Perovskite type RE-doped NaTaO₃ (where RE represents Rare Earths elements like Y, La, Ce, Yb) catalysts, derived from solid state synthesis method, have been used for the photocatalytic hydrogen production from water using methanol as sacrificial agent. The photocatalytic activity of NaTaO₃ in H₂ production is improved on its doping with Y, La or Yb elements. In contrast, Ce-doped sample shows a worsening of the photoactivity, which is even lower than the un-doped catalyst. The characterization of the materials reveals that the monoclinic structure and the presence of Ce⁴⁺ do not favour to increase the performance of NaTaO₃. Previous reports proved that La-doping boosted the water splitting photoactivity of NaTaO₃. However the results of this work reveal an increase in the H₂ production by the use of Y as dopant. This enhancement in the photoactivity could be related with the modification of the opto-electronic properties of NaTaO₃ with the inclusion of RE elements (Y, La, Yb) in the orthorhombic structure of this perovskite. Moreover, the catalytic activity of all the RE-doped samples is further increased on their modification with Pt nanoparticles (NPs) loading that act as photo-generated electron scavenger facilitating the reduction reactions.     

New fan blade-like core-shell Sb2TixSy photocatalytic nanorod for hydrogen production from methanol/water photolysis

New photocatalysts of Sb₂Ti_xS_y (x = 0, 0.5, 1.0, 1.5 mol and y = 3, 4, 5, 6 mol) fan blade-like core-shell nanorods have been designed ultimately to enhance hydrogen production. The nanorods of 500 nm long and 60–100 nm wide are Sb₂S₃ nanorod surrounded by an amorphous TiS₂ membrane, showing absorption band edges of above 600 nm. The evolution of H₂ from methanol/water (1:1) photo-splitting over Sb₂Ti_xS_y nanorods in the liquid system is doubled, compared to that over pure Sb₂S₃. Particularly, 52 μmol of H₂ gas is produced after 10 h when 0.5 g of Sb₂Ti_1.0S₅ nanorods is used at pH = 7, and the performance is increased by more than 50% at higher pH. Based on cyclic voltammetry (CV) and UV-Visible absorption spectra, the high photocatalytic activity can be attributed to the existence of an appropriate band-gap state, which includes the scope of the redox potential of water in Sb₂Ti_1.0S₅ nanorods, resulting in the promotion of the redox reaction of water.     

Photocatalytic hydrogen production from water/methanol solutions over highly ordered Ag-SrTiO3 nanotube arrays

The highly ordered Ag-SrTiO₃ nanotube arrays (NTAs) with uniform size were successfully synthesized by a combination of anodic oxidation, hydrothermal process and photocatalytic reduction method. X-ray photoelectron spectroscopy analysis reveals that Ag exists in the form of metallic silver, which is in good agreement with the X-ray diffraction characterization. Moreover, the UV-vis diffuse reflectance spectra indicate that Ag-SrTiO₃ NTAs have a strong absorption in the visible region which is attributed to the plasmon resonance of silver nanoparticles. After Ag loading, a further improvement of the photocatalytic activity for hydrogen production was obtained. Based on the above results, a possible electron-hole transfer mechanism was also assumed.     

Electrolytic production of hydrogen from aqueous acidic methanol solutions

The electrochemical production of hydrogen (H₂) from liquid methanol in acidic aqueous media was investigated in a proton exchange membrane (PEM) electrolyser, comprising a two-compartment glass cell with a membrane electrode assembly (MEA) composed of a Nafion^® 117 membrane and gas diffusion electrodes (GDE). Methanol electrolysis was studied at concentrations ranging from 0 to 16 M, where 0 M corresponds to water electrolysis. The influence of catalysts (Pt and Pt–Ru), catalyst support (C or black), operating temperatures (23, 50 and 75 °C) and operating modes (dry and wet cathode) were evaluated in the static mode. A theoretical thermodynamic analysis of the system was done as a function of temperature. The limiting current densities, kinetic parameters, including the Tafel slopes and current exchange density, and apparent activation energies were determined.     

Absorption enhanced reforming of light alcohols (methanol and ethanol) for the production of hydrogen: Thermodynamic modeling

Thermodynamic modeling of the steam reforming of light alcohols using CaO, CaO*MgO, Na₂ZrO₃, Li₂ZrO₃ and Li₄SiO₄ as CO₂ absorbents was carried out to determine promising operating conditions to produce a high hydrogen yield (YH₂)$\left(Y_{{\text{H}}_2}\right)$ and concentration (% H₂). Ethanol and methanol were studied at 300–800 °C and 1 atm. Steam to alcohol (S/COH) feed molar ratio varied from 1:1 (stoichiometric) to 6:1 for methanol and from 3:1 (stoichiometric) to 6:1 for ethanol. Thermodynamic simulations employed the Gibbs free energy minimization technique. Results indicate no carbon formation at S/COH ≤ stoichiometric. For both alcohols reforming at 600 °C and S/COH = 6, using CaO, CaO*MgO, and Na₂ZrO₃ produced optimal YH₂$Y_{{\text{H}}_2}$ and hydrogen purity (% H₂). In both reforming systems most favorable thermodynamics were obtained with CaO, CaO*MgO and Na₂ZrO₃ as absorbents. A Thermal efficiency analysis performed in all system confirmed the superiority of the CO₂ absorption systems against conventional reforming processes.     

Sorbent enhanced hydrogen production from steam gasification of coal integrated with CO2 capture

In this work, CO₂ capture and H₂ production during the steam gasification of coal integrated with CO₂ capture sorbent were investigated using a horizontal fixed bed reactor at atmospheric pressure. Four different temperatures (650, 675, 700, and 750 °C) and three sorbent-to-carbon ratios ([Ca]/[C] = 0, 1, 2) were studied. In the absence of sorbent, the maximum molar fraction of H₂ (64.6%) and conversion of coal (71.3%) were exhibited at the highest temperature (750 °C). The experimental results verified that the presence of sorbent in the steam gasification of coal enhanced the molar fraction of H₂ to more than 80%, with almost all CO₂ was fixed into the sorbent structure, and carbon monoxide (CO) was converted to H₂ and CO₂ through the water gas shift reaction. The steam gasification of coal integrated with CO₂ capture largely depended on the reaction temperature and exhibited optimal conditions at 675 °C. The maximum molar fraction of H₂ (81.7%) and minimum CO₂ concentration (almost 0%) were obtained at 675 °C and a sorbent-to-carbon ratio of 2.     

Process simulation and optimization of methanol production coupled to tri-reforming process

Tri-reforming, as a new approach for the treatment of CO₂ in flue stack gases, has been studied in this work. To determine the optimum operating conditions for the production of syngas with target ratio and maximum CO₂ conversion, the effects of temperature (400–1200 °C), CH₄/Flue gas ratio (0.4–1.0) and pressure (1–5 atm), on the compositions of syngas were investigated. Also, the methanol production from syngas has been rigorously simulated. An optimum heat exchange network was obtained with the objective of minimizing both utility and capital costs, which were calculated by General Algebraic Modeling system (GAMS). Furthermore, an economic analysis was carried out to substantiate the potential profits based on the conceptual results from heat integration. Results showed that the tri-reforming process, when integrated with methanol synthesis, is an economical approach for the treatment and utilization of CO₂ in flue gases.     

Photocatalytic hydrogen production over CuGa2−xFexO4 spinel

Recovery of hydrogen from industrial H₂S waste using spinel photocatalyst was studied. Spinel metal oxide photocatalysts (CuGa_2−xFe_xO₄ for x = 0.8, 0.6 and 0.4) were synthesized by ceramic route. They were loaded with 0.5 and 1 wt% noble metal oxide, RuO_2. Their XRD pattern revealed a single phase cubic spinel crystalline structure for all the catalysts. SEM displayed small size cubic particles with the particle size decreasing with the decrease in iron content. 1 wt% RuO₂ loaded CuGa_1.6Fe_0.4O₄ decomposed H₂S in aqueous 0.5 M KOH solution under visible light (λ ≥ 420 nm) irradiation and generated H₂ to the tune of 10,045 μmol/h, giving rise to a high quantum efficiency of 21% at 510 nm.     

Photo-catalytic hydrogen production over Fe2O3 based catalysts

The hydrogen photo-evolution was successfully achieved in aqueous (Fe_1−xCr_x)₂O₃ suspensions (0 ≤ x ≤ 1). The solid solution has been prepared by incipient wetness impregnation and characterized by X-ray diffraction, BET, transport properties and photo-electrochemistry. The oxides crystallize in the corundum structure, they exhibit n-type conductivity with activation energy of ∼0.1 eV and the conduction occurs via adiabatic polaron hops. The characterization of the band edges has been studied by the Mott Schottky plots. The onset potential of the photo-current is ∼0.2 V cathodic with respect to the flat band potential, implying a small existence of surface states within the gap region. The absorption of visible light promotes electrons into (Fe_1−xCr_x)₂O₃-CB with a potential (∼−0.5 V_SCE) sufficient to reduce water into hydrogen. As expected, the quantum yield increases with decreasing the electro affinity through the substitution of iron by the more electropositive chromium which increases the band bending at the interface and favours the charge separation. The generated photo-voltage was sufficient to promote simultaneously H₂O reduction and SO₃²⁻ oxidation in the energetically downhill reaction (H₂O + SO₃²⁻ → H₂ + SO₄²⁻, ΔG = −17.68 kJ mol⁻¹). The best activity occurs over Fe_1.2Cr_0.8O₃ in SO₃²⁻ (0.1 M) solution with H₂ liberation rate of 21.7 μmol g⁻¹ min⁻¹ and a quantum yield 0.06% under polychromatic light. Over time, a pronounced deceleration occurs, due to the competitive reduction of the end product S₂O₆²⁻.     

Microbial hydrogen production from sewage sludge bioaugmented with a constructed microbial consortium

A constructed microbial consortium was formulated from three facultative H₂-producing anaerobic bacteria, Enterobacter cloacae IIT-BT 08, Citrobacter freundii IIT-BT L139 and Bacillus coagulans IIT-BT S1. This consortium was tested as the seed culture for H₂ production. In the initial studies with defined medium (MYG), E. cloacae produced more H₂ than the other two strains and it also was found to be the dominant member when consortium was used. On the other hand, B. coagulans as a pure culture gave better H₂ yield (37.16 ml H₂/g COD_consumed) than the other two strains using sewage sludge as substrate. The pretreatment of sludge included sterilization (15% v/v), dilution and supplementation with 0.5% w/v glucose, which was found to be essential to screen out the H₂ consuming bacteria and ameliorate the H₂ production. Considering (1:1:1) defined consortium as inoculum, COD reduction was higher and yield of H₂ was recorded to be 41.23 ml H₂/g COD_reduced. Microbial profiling of the spent sludge showed that B. coagulans was the dominant member in the constructed consortium contributing towards H₂ production. Increase in H₂ yield indicated that in consortium, the substrate utilization was significantly higher. The H₂ yield from pretreated sludge (35.54 ml H₂/g sludge) was comparatively higher than that reported in literature (8.1–16.9 ml H₂/g sludge). Employing formulated microbial consortium for biohydrogen production is a successful attempt to augment the H₂ yield from sewage sludge.     

Thermodynamic analysis of combined unit of biomass gasifier and tar steam reformer for hydrogen production and tar removal

A combined unit of biomass gasifier and tar steam reformer (CGR) was proposed in this study to achieve simultaneous tar removal and increased hydrogen production. Tar steam reforming calculations based on thermodynamic equilibrium were carried out by using Aspen Plus software. Thermodynamic analysis reveals that when selecting appropriate operating conditions, exothermic heat available from the gasifier could sufficiently supply to the heat-demanding units including feed preheaters, steam generator and reformer. The effects of gasification temperature (T_gs), reforming temperature (T_ref) and steam-to-biomass ratio (S:BM) on percentages of tar removal and improvement of H₂ production were investigated. It was reported that the CGR system can completely remove tar and increase H₂ production (1.6 times) under thermally self-sufficient condition. The increase of H₂ production is mainly via the water–gas shift reaction.     

Visible light photocatalytic water splitting for hydrogen production from N-TiO2 rice grain shaped electrospun nanostructures

We report on the visible light-driven hydrogen production from splitting of water molecules by nitrogen-doped TiO₂ (N-TiO₂) with a rice grain-like nanostructure morphology. The N-TiO₂ nanostructures are prepared using sol-gel and electrospinning methods followed by post-annealing of the composite nanofibers. The nanostructures are characterized by microscopy and spectroscopy. First order rate constants for the visible light-assisted photocatalysis in the degradation of methylene blue (MB) dye are found to be 0.2 × 10⁻³ and 1.8 × 10⁻³ min⁻¹ for TiO₂ and N-TiO₂ (5 wt% of nitrogen), respectively. The N-TiO₂ utilized in water splitting experiments and evaluated hydrogen (H₂) of 28 and 2 μmol/h for N-TiO₂ and TiO₂, respectively. The improvement may be attributed due to the N-doping and higher surface area as ∼70 m²/g.