Hydrogen generation from the hydrolysis of ammonia borane using cobalt-nickel-phosphorus (Co-Ni-P) catalyst supported on Pd-activated TiO2 by electroless deposition

Catalytically active, low-cost, and reusable transition metal catalysts are desired to develop on-demand hydrogen generation system for practical onboard applications. By using electroless deposition method, we have prepared the Pd-activated TiO₂-supported Co-Ni-P ternary alloy catalyst (Co-Ni-P/Pd-TiO₂) that can effectively promote the hydrogen release from ammonia-borane aqueous solution. Co-Ni-P/Pd-TiO₂ catalysts are stable enough to be isolated as solid materials and characterized by XRD, SEM, and EDX. They are isolable, redispersible and reusable as an active catalyst in the hydrolysis of AB. The reported work also includes the full experimental details for the collection of a wealth of kinetic data to determine the activation energy (E_a = 54.9 kJ mol⁻¹) and effects of the amount of catalyst, amount of substrate, and temperature on the rate for the catalytic hydrolysis of AB. Maximum H₂ generation rate of ∼60 mL H₂ min⁻¹ (g catalyst)⁻¹ and ∼400 mL H₂ min⁻¹ (g catalyst)⁻¹ was measured by the hydrolysis of AB at 25 °C and 55 °C, respectively.     

Hydroxyapatite-supported palladium(0) nanoclusters as effective and reusable catalyst for hydrogen generation from the hydrolysis of ammonia-borane

Herein we report the preparation, characterization and catalytic use of hydroxyapatite-supported palladium(0) nanoclusters in the hydrolysis of ammonia-borane. Palladium(0) nanoclusters were formed in situ from the reduction of palladium(II) ion exchanged hydroxyapatite during the hydrolysis of ammonia-borane and supported on hydroxyapatite. The hydroxyapatite-supported palladium(0) nanoclusters are stable enough to be isolated as solid materials and characterized by using a combination of advanced analytical techniques. They are isolable, redispersible and reusable as an active catalyst in the hydrolysis of ammonia-borane even at low concentration and temperature. They provide a maximum hydrogen generation rate of ∼1425 mL H₂ min⁻¹ (g Pd)⁻¹ and 12300 turnovers in the hydrolysis of ammonia-borane at 25 ± 0.1 °C before deactivation. The work reported here also includes the full experimental details for the collection of a wealth of kinetic data to determine the activation energy (E_a = 54.8 ± 2.2 kJ/mol) and the effect of catalyst concentration on the rate for the catalytic hydrolysis of ammonia-borane.     

Pd-Gardenia-TiO2 as a photocatalyst for H2 evolution from pure water

The photocatalytic activity for H₂ evolution from pure water over Pd loaded TiO₂ prepared by gardenia extract (Pd-Gardenia-TiO₂) is systematically investigated. The as-prepared photocatalysts are characterized by X-ray diffraction, high resolution transmission electron microscopy, Fourier transform infrared spectra, and X-ray photoelectron spectroscopy. Gardenia extract functions as reducing and stabilizing agents simultaneously. The mean size of the as-prepared Pd nanoparticles is in the range of 2.3 ± 0.5 nm based on TEM images. The Pd-Gardenia-TiO₂ catalyst exhibits good photocatalytic activity for H₂ evolution (93 μmol · h⁻¹ · g⁻¹), which is much higher than that of Pd photodeposited on TiO₂. Possible factors for its photocatalytic activity from pure water are also investigated.     

In situ facile synthesis of ruthenium nanocluster catalyst supported on carbon black for hydrogen generation from the hydrolysis of ammonia-borane

Ligand-free Ru nanoclusters supported on carbon black have been synthesized in situ for the first time from the reduction of RuCl₃ by ammonia-borane concomitantly with its hydrolysis process at room temperature, and their catalytic activity has been investigated. Well dispersed Ru nanoclusters (∼1.7 nm) are stabilized and immobilized by carbon black. Due to the small size and the absence of ligands on the surface, the Ru catalysts exhibit high catalytic activity, which is partly retained after 5 reaction cycles. A kinetic study shows that the catalytic hydrolysis of ammonia-borane is first order with respect to Ru catalyst concentration; the turnover frequency is 429.5 mol H₂ min⁻¹ mol⁻¹ Ru. The activation energy for the hydrolysis of ammonia-borane in the presence of Ru/C catalysts has been measured to be 34.81 ± 0.12 kJ mol⁻¹, which is smaller than most of the values reported for other catalysts, including those based on Ru, for the same reaction.     

Solution combustion synthesized cobalt oxide catalyst precursor for NaBH4 hydrolysis

In this paper we report the solution combustion synthesis of cobalt oxide nanofoam from solutions of cobalt nitrate and glycine and subsequent use as an effective catalyst precursor for NaBH₄ hydrolysis. The catalytic activity results show that the hydrogen generation rate (HGR) at room temperature was much higher for the solution combustion synthesized material than for commercial Co₃O₄ nanopowder, though their specific surface areas were comparable (∼26–32 m²/g). Using a 0.6 wt.% aqueous solution of NaBH₄ at 20 °C and a 5 wt.% catalyst precursor loading, a HGR of 1.93 L min⁻¹ g_cat⁻¹ was achieved for solution combustion synthesized Co₃O₄. In contrast, at the same conditions, for commercial Co₃O₄ and elemental Co powders HGRs of 0.98 and 0.49 L min⁻¹ g_cat⁻¹ were achieved respectively. This type of synthesis is amenable to many complex metal oxide catalysts as well, such as LiCoO₂, which have also been shown to be good catalyst precursors for hydrolysis of NaBH₄.     

Low-temperature preparation of AgIn5S8/TiO2 heterojunction nanocomposite with efficient visible-light-driven hydrogen production

AgIn₅S₈ and AgIn₅S₈/TiO₂ heterojunction nanocomposite with efficient photoactivity for H₂ production were prepared by a low-temperature water bath deposition process. The resultant AgIn₅S₈ shows an absorption edge at ∼720 nm, corresponding to a bandgap of ∼1.72 eV, and its visible-light-driven photoactivity (100.1 μmol h⁻¹) for H₂ evolution is 9 times higher than that (11 μmol h⁻¹) of the product derived from a hydrothermal process, while the obtained AgIn₅S₈/TiO₂ heterojunction nanocomposites prepared by using commercially available TiO₂ nanoparticles (P25) as TiO₂ source exhibit remarkably improved photoactivity as compared to the pristine AgIn₅S₈, and the AgIn₅S₈/TiO₂ nanocomposite with molar ratio of 1:10 shows a maximum photocatalytic H₂ evolution rate (371.1 μmol h⁻¹), which is 4.3 times higher than that (85 μmol h⁻¹) of the corresponding AgIn₅S₈/TiO₂ nanocomposite derived from a hydrothermal method. This significant enhancement in the photocatativity of the present AgIn₅S₈/TiO₂ nanocomposite can be ascribed to the better dispersion of the AgIn₅S₈ formed on TiO₂ nanoparticle surfaces and the more intimate AgIn₅S₈/TiO₂ heterojunction structure during the water bath deposition process under continuously stirring as compared to the corresponding nanocomposite derived from a hydrothermal method. This configuration of nanocomposite results in fast diffusion of the photogenerated carriers in AgIn₅S₈ towards TiO₂, which is beneficial for separating spatially the photogenerated carriers and improving the photoactivity. The present findings shed light on the tuning strategy of spectral responsive region and photoactivity of photocatalysts for efficient light-to-energy conversion.     

Carbon-incorporated TiO2 photoelectrodes prepared via rapid-anodic oxidation for efficient visible-light hydrogen generation

Carbon-incorporated titanium dioxide (TiO₂) photoelectrodes with different structural features were prepared via rapid-anodic oxidation under different electrical potentials and exposure times. The interstitial carbon arising from the pyrogenation of ethylene glycol electrolytes induced a new C2p occupied state at the bottom of the conduction band, which lowered the band gap energy to ∼2.3 eV and consequently enabled the visible-light responsiveness. Photoelectrodes with nanotubular structures provided higher photoconversion efficiency (η) and hydrogen (H₂) evolution capability than those with irregular structures. The increased aspect ratio, wall thickness, and pore size of the nanotube arrays contributed to η through greater photon excitation and penetration. However, this contribution is limited by the high recombination of the charge carriers at ultra-high aspect ratios. Photoelectrodes with a nanotube length of ∼19.5 μm, pore size of ∼103 nm, wall thickness of ∼17 nm, and aspect ratio of ∼142.5 exhibited remarkable capability to generate H₂ at an evolution rate of up to ∼508.3 μL min⁻¹ cm⁻² and η of ∼2.3%.     

Metal nanoparticle-embedded super porous poly(3-sulfopropyl methacrylate) cryogel for H2 production from chemical hydride hydrolysis

Poly(3-sulfopropyl methacrylate) (p(SPM)) cryogel was prepared under cryogenic conditions (T = −18 °C) and used as template for in situ metal nanoparticle preparation of Co, Ni and Cu. These metal nanoparticle-containing super macroporous cryogel composites were tested for H₂ production from hydrolysis of sodium borohydride (NaBH₄) and ammonia borane (AB). It was found that amongst p(SPM)-M (M: Co, Ni, and Cu) composite catalyst systems, the catalytic performances of Co- and Ni-containing p(SPM) cryogel composite catalyst systems were the same, however in hydrolysis of NH₃BH₃, the order of performance of the catalysts was Co > Ni > Cu. Interestingly, p(SPM)-Co cryogel composite demonstrated better catalytic performances in salt environments e.g., faster H₂ production rate in sea and tap water compared to DI water, and almost no effect of ionic strength of the solution medium was observed, but the salt types were found to affect the H₂ generation rate. Other parameters that affect H₂ production rate such as metal type, temperature, water source, salt concentration, amount of metal nanocatalyst and reusability were investigated. It was found that the hydrogen generation rate (HGR) was increased to 2836 ± 90 from 1000 ± 53 (ml H₂)(g of Co min)⁻¹ by multiple loading and reduction cycles of Co catalyst. Also, it was found that TOF values are highly temperature dependent, and increased to 15.1 ± 0.8 from 2.4 ± 0.1 (mol H₂)(mol catalyst min)⁻¹ by increasing the temperature from 30 to 70 °C. The activation energy, activation enthalpy and activation entropy were determined as 40.8 kJ (mol)⁻¹, 37.23 kJ (mol K)⁻¹, and −170.87 J (mol K)⁻¹, respectively, for the hydrolysis reaction of NaBH₄ with p(SPM)-Co catalyst system, and 25.03 kJ (mol)⁻¹, 22.41 kJ (mol K)⁻¹, and −182.8 J (mol K)⁻¹, respectively, for AB hydrolysis catalyzed by p(SPM)-Co composite system.     

Superporous P(2-hydroxyethyl methacrylate) cryogel-M (M:Co,Ni, Cu) composites as highly effective catalysts in H2 generation from hydrolysis of NaBH4 and NH3BH3

Highly porous p(2-hydroxyethyl methacrylate) p(HEMA) cryogels were synthesized via cryopolymerization technique and used as template for Co, Ni, and Cu nanoparticle preparation, then as composite catalyst systems in H₂ generation from hydrolysis of both NaBH₄ and NH₃BH₃. Due to their highly porous and open microstructures, p(HEMA)-Co cryogel composites showed very effective performances in H₂ production from hydrolysis of both chemical hydrides. The characterization of p(HEMA) cryogels, and their metal composites was determined via various techniques including swelling experiments, digital camera images, SEM and TEM images, AAS and TGA measurements. The effect of various parameters on the hydrolysis reaction of NaBH₄ such as metal types, concentration of chemical hydrides, amounts of catalyst, alkalinity of reaction medium and temperature were investigated in detail. It was found that Co nanoparticles are highly active catalysts in H₂ generation reactions from both hydrides. The hydrogen generation rate (HGR) of p(HEMA)-Co was 1596 (mL H₂) (min)⁻¹ (g of Co)⁻¹ which is quite good in comparison to reported values in the literature. Furthermore, kinetic parameters of p(HEMA)-Co metal composites such as energy, enthalpy and entropy were determined as Ea = 37.01 kJmol⁻¹, ΔH# = 34.26 kJmol⁻¹, ΔS# = −176,43 Jmol⁻¹ K⁻¹, respectively.     

Hydrogen storage properties of nanostructured MgH2/TiH2 composite prepared by ball milling under high hydrogen pressure

Nanostructured MgH₂/0.1TiH₂ composite was synthesized directly from Mg and Ti metal by ball milling under an initial hydrogen pressure of 30 MPa. The synthesized composite shows interesting hydrogen storage properties. The desorption temperature is more than 100 °C lower compared to commercial MgH₂ from TG-DSC measurements. After desorption, the composite sample absorbs hydrogen at 100 °C to a capacity of 4 mass% in 4 h and may even absorb hydrogen at 40 °C. The improved properties are due to the catalyst and nanostructure introduced during high pressure ball milling. From the PCI results at 269, 280, 289 and 301 °C, the enthalpy change and entropy change during the desorption can be determined according to the van’t Hoff equation. The values for the MgH₂/0.1TiH₂ nano-composite system are 77.4 kJ mol⁻¹ H₂ and 137.5 J K⁻¹ mol⁻¹ H₂, respectively. These values are in agreement with those obtained for a commercial MgH₂ system measured under the same conditions. Nanostructure and catalyst may greatly improve the kinetics, but do not change the thermodynamics of the materials.     

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⁻.     

An improvement of the hydrogen permeability of C/Al2O3 membranes by palladium deposition into the pores

The development of compact hydrogen separator based on membrane technology is of key importance for hydrogen energy utilization, and the Pd-modified carbon membranes with enhanced hydrogen permeability were investigated in this work. The C/Al₂O₃ membranes were prepared by coating and carbonization of polyfurfuryl alcohol, then the palladium was introduced through impregnation–precipitation and colloid impregnation methods with a PdCl₂/HCl solution and a Pd(OH)₂ colloid as the palladium resources, and the reduction was carried out with a N₂H₄ solution. The resulting Pd/C/Al₂O₃ membranes were characterized by means of SEM, EDX, XRD, XPS and TEM, and their permeation performances were tested with H₂, CO₂, N₂ and CH₄ at 25 °C. Compared with the colloid impregnation method, the impregnation–precipitation is more effective in deposition of palladium clusters inside of the carbon layer, and this kind of Pd/C/Al₂O₃ membranes exhibits excellent hydrogen permeability and permselectivity. Best hydrogen permeance, 1.9 × 10⁻⁷ mol/m² s Pa, is observed at Pd/C = 0.1 wt/wt, and the corresponding H₂/N₂, H₂/CO₂ and H₂/CH₄ permselectivities are 275, 15 and 317, respectively.     

Hydrogen generation by hydrolysis of sodium borohydride on CoB/SiO2 catalyst

Generation of hydrogen by hydrolysis of alkali metal hydrides has attracted attention. Unsupported CoB catalyst demonstrated high activity for the catalytic hydrolysis of NaBH₄ solution. However, unsupported CoB nanoparticles were easy to aggregate and difficult to reuse. To overcome these drawbacks, CoB/SiO₂ was prepared and tested for this reaction. Cobalt (II) acetate precursor was loaded onto the SiO₂ support by incipient-wetness impregnation method. After drying at 100 °C, Co cations were deposited on the support. The dried sample was then dispersed in methanol/water solution and then fully reduced by NaBH₄ at room temperature. The catalyst was characterized by N₂ sorption, XRD and XPS. The results indicated that the CoB on SiO₂ possessed amorphous structure. B and Co existed both in elemental and oxidized states. SiO₂ not only affected the surface compositions of CoB, but also affected the electronic states of Co and B. B⁰ could donate partial electron to Co⁰. The structure effect caused by the SiO₂ support helped to prevent CoB nanocluster from aggregation and therefore the activity increased significantly on hydrolysis of alkaline NaBH₄ solution. The CoB/SiO₂ catalyst showed much higher activity than the unsupported CoB catalyst. At 298 K, the hydrogen generation rate on CoB/SiO₂ catalyst was 4 times more than that on the unsupported CoB catalyst. The hydrogen generation rate was as high as 10,586 mL min⁻¹ g⁻¹ catalyst at 298 K. CoB/SiO₂ is a very promising catalyst for this reaction.     

Monodispersed p(2-VP) and p(2-VP-co-4-VP) particle preparation and their use as template for metal nanoparticle and as catalyst for H2 production from NaBH4 and NH3BH3 hydrolysis

The monodispersed poly(2-vinyl pyridine) (p(2-VP)) and poly(2-vinyl pyridine-co-4-vinyl pyridine) (p(2-VP-co-4-VP)) particles of different compositions were synthesized by a surfactant-free emulsion polymerization system using divinyl benzene (DVB) as cross-linker. The diameter of p(2-VP) and p(2-VP-co-4-VP) particles were measured between 370 and 530 nm. Co, Ni and Cu metal nanoparticles were prepared inside these microgels after quaternization with HCl and loading of metal salts, such as CoCl₂, NiCl₂, and CuCl₂, in ethyl alcohol followed by reduction with NaBH₄. The prepared metal nanoparticles within these particles were used as catalyst for H₂ production via hydrolysis of NaBH₄ and NH₃BH₃. Various parameters of the polymeric microgels such as template, metal types, reuse, the amount of NaOH, and temperature were investigated. From hydrolysis reactions the activation energy (E_a), enthalpy (ΔH), and entropy (ΔS) were calculated for Co metal nanoparticles as catalyst for the NaBH₄ hydrolysis reaction in the temperature range of 0–50 °C. The activation parameters of NaBH₄ hydrolysis catalyzed by Co nanoparticle composite systems were calculated as 46.44 ± 1.1 kJ mol⁻¹ for E_a, 36.39 ± 6.5 kJ mol⁻¹ for ΔH and −170.56 ± 20.1 kJ mol⁻¹ K⁻¹ for ΔS.     

Improved hydrogen storage performance of Mg(NH2)2/LiH mixture by addition of carbon nanostructured materials

The effect of different carbon nanostructures specifically carbon nanotubes (CNTs) and carbon nanofibers (CNFs) on the improvement of the de/re-hydrogenation characteristics of a Mg(NH₂)₂/LiH mixture have been studied. Amongst CNTs and CNFs, the improvement in the hydrogenation properties for the Mg(NH₂)₂/LiH mixture is higher when CNFs are used as a catalyst. Investigations are also focused on the deployment of two different types of CNF (a) CNF1 (synthesized using a ZrFe₂ catalyst) and (b) CNF2 (synthesized using a LaNi₅ catalyst). The results show that CNF2 is better. The maximum decomposition temperature for the pristine Mg(NH₂)₂/LiH mixture is found to be ∼250 °C, which is reduced to ∼180 and ∼150 °C for the sample mixed with 4 wt% of multi-walled carbon nanotubes (MWCNTs) and CNF2 respectively. The activation energy for the dehydrogenation reaction is found to be 74 and 68 kJ mol⁻¹ for the samples mixed with MWCNT and CNF2 respectively, whereas the activation energy for the dehydrogenation reaction of the pristine Mg(NH₂)₂/LiH mixture is 97 kJ mol⁻¹. The catalytic activity and the de/re-hydrogenation characteristics of the Mg(NH₂)₂/LiH mixture mixed with different carbon nanostructures are described and discussed.     

H2 production via water gas shift in a composite Pd membrane reactor prepared by the pore-plating method

In this work, H₂ production via catalytic water gas shift reaction in a composite Pd membrane reactor prepared by the ELP “pore-plating” method has been carried out. A completely dense membrane with a Pd thickness of about 10.2 μm over oxidized porous stainless steel support has been prepared. Firstly, permeation measurements with pure gases (H₂ and N₂) and mixtures (H₂ with N_2, CO or CO₂) at four different temperatures (ranging from 350 to 450 °C) and trans-membrane pressure differences up to 2.5 bar have been carried out. The hydrogen permeance when feeding pure hydrogen is within the range 2.68–3.96·10⁻⁴ mol m⁻² s⁻¹ Pa^−0.5, while it decreases until 0.66–1.35·10⁻⁴ mol m⁻² s⁻¹ Pa^−0.5 for gas mixtures. Furthermore, the membrane has been also tested in a WGS membrane reactor packed with a commercial oxide Fe–Cr catalyst by using a typical methane reformer outlet (dry basis: 70%H₂–18%CO–12%CO₂) and a stoichiometric H₂O/CO ratio. The performance of the reactor was evaluated in terms of CO conversion at different temperatures (ranging from 350 °C to 400 °C) and trans-membrane pressures (from 2.0 to 3.0 bar), at fixed gas hourly space velocity (GHSV) of 5000 h⁻¹. At these conditions, the membrane maintained its integrity and the membrane reactor was able to achieve up to the 59% of CO conversion as compared with 32% of CO conversion reached with conventional packed-bed reactor at the same operating conditions.     

Production of an Mg/Mg2Ni lamellar composite for generating H2 and the recycling of the post-H2 generation residue to nickel powder

The magnesium hydrolyzing reaction was catalyzed in situ using a layered Mg₂Ni compound, rapidly producing hydrogen in NaCl solution. The post-H₂ generation residue (mixture of Mg(OH)₂ and Mg₂Ni catalyst) was recycled to recover pure Ni powder from the waste mixture. Pure Mg (153 g) and pure Ni (47 g) in a eutectic composition were easily melted to form a molten alloy by a super-high-frequency (35,000 Hz) induction furnace. The lamellar material had an Mg/Mg₂Ni/Mg/Mg₂Ni… layered structure, in which each layer was ∼0.8 μm thick; Mg was an anodic phase and Mg₂Ni was a cathodic phase (the catalyst). Bulk Mg/Mg₂Ni composite alloy contains many microgalvanic cells. Owing to the lamellar microstructure, no dense hydrated oxide film that might have caused surface passivation was found, allowing continuous H₂ generation until no magnesium remained to participate in the hydrolysis. The activation energy of the hydrolysis reaction in simulated sea water was ∼36.35 kJ mol⁻¹.     

Pd nanoparticles supported on MIL-101 as high-performance catalysts for catalytic hydrolysis of ammonia borane

Well dispersed ultrafine Pd NPs have been immobilized in the framework of MIL-101, and tested for the catalytic hydrolysis of ammonia borane. The powder XRD, N₂ adsorption–desorption, TEM, and ICP-AES were employed to characterize the Pd@MIL-101 catalyst. The as-synthesized Pd@MIL-101 exhibit the highest catalytic activity toward hydrolysis of AB among the Pd-based nano-catalysts ever reported, with the TOF value of 45 mol H₂ min⁻¹ (mol Pd)⁻¹.     

g-C3N4 coated SrTiO3 as an efficient photocatalyst for H2 production in aqueous solution under visible light irradiation

A highly active photocatalyst based on g-C₃N₄ coated SrTiO₃ has been synthesized simply by decomposing urea in the presence of SrTiO₃ at 400 °C. The catalyst demonstrates a high H₂ production rate ∼440 μmol h⁻¹/g catalyst in aqueous solution under visible light irradiation, which is much higher than conventional anion doped SrTiO₃ or physical mixtures of g-C₃N₄ and SrTiO₃. The improved photocatalytic activity can be ascribed to the close interfacial connections between g-C₃N₄ and SrTiO₃ where photo-generated electron and holes are effectively separated. The newly synthesized catalyst also exhibited a stable performance in the repeated experiments.     

H2 production by γ and He ions water radiolysis, effect of presence TiO2 nanoparticles

The effect of TiO₂ particles on the yield of H₂ formation under water radiolysis is measured. Irradiations were performed using a ⁶⁰Co γ−ray source as well as with He ions particles (4He2⁺) generated by a cyclotron with an external beam energy of 6 MeV. The resulting hydrogen as a stable product of radiolysis was measured by mass spectrometry. G(H₂) obtained for water radiolysis by He ions−irradiation in aerated and argon water are found to be 1.91 × 10⁻⁷ and 1.35 × 10⁻⁷ mol J⁻¹, respectively. In the presence of titanium oxide anatase−type dispersed in water, under He ions−irradiation, G(H₂) is found to increase slightly from 1.04 × 10⁻⁷ to 1.35 × 10⁻⁷ mol J⁻¹ by increasing the specific surface from 8 to 253 m²/g, respectively. Under γ-irradiation, G(H₂) is found to be 0.41 × 10⁻⁷ mol J⁻¹ close to primary yield of hydrogen in presence of OH. Radical scavenger. In addition, radiolysis of water adsorbed in the titanium oxide with low water content, which corresponds to a few layers of water sorbed onto the solid surface gives a huge values of the G(H₂). For the same amount of water, with using the dose absorbed by TiO₂ particles, for He ions-irradiation, G(H₂) increases from 14.5 × 10⁻⁷ to 35 × 10⁻⁷ mol J^-1 by increasing the surface area of TiO₂ nanoparticles from 4 to 52 m²/g, respectively. For γ−irradiation G(H₂) is found to be 5.25 × 10⁻⁷ mol J^-1 for the sample with 8 m²/g specific surface area.