Catalytic hydrolysis of ammonia borane: Intrinsic parameter estimation and validation

Ammonia borane (AB) hydrolysis is a potential process for on-board hydrogen generation. This paper presents isothermal hydrogen release rate measurements of dilute AB (1 wt%) hydrolysis in the presence of carbon supported ruthenium catalyst (Ru/C). The ranges of investigated catalyst particle sizes and temperature were 20-181 μm and 26-56 °C, respectively. The obtained rate data included both kinetic and diffusion-controlled regimes, where the latter was evaluated using the catalyst effectiveness approach. A Langmuir-Hinshelwood kinetic model was adopted to interpret the data, with intrinsic kinetic and diffusion parameters determined by a nonlinear fitting algorithm. The AB hydrolysis was found to have an activation energy 60.4 kJ mol⁻¹, pre-exponential factor 1.36 × 10¹⁰ mol (kg-cat)⁻¹ s⁻¹, adsorption energy −32.5 kJ mol⁻¹, and effective mass diffusion coefficient 2 × 10⁻¹⁰ m² s⁻¹. These parameters, obtained under dilute AB conditions, were validated by comparing measurements with simulations of AB consumption rates during the hydrolysis of concentrated AB solutions (5-20 wt%), and also with the axial temperature distribution in a 0.5 kW continuous-flow packed-bed reactor.     

Hydrogen generation by hydrolysis of ammonia borane with a nanoporous cobalt-tungsten-boron-phosphorus catalyst supported on Ni foam

In this study, quaternary cobalt-tungsten-boron-phosphorus porous particles supported on Ni foam (Co-W-B-P/Ni), which are prepared through ultrasonification-assisted electroless deposition route, have been investigated as the catalyst for hydrogen generation (HG) from hydrolysis of ammonia borane (NH₃BH₃, AB). Compared with Ni-supported binary Co-B and ternary Co-W-B catalysts, the as-synthesized Co-W-B-P/Ni shows a higher HG rate. To optimize the preparation parameters, the molar ratio of NaBH₄/NaH₂PO₂·H₂O (B/P) and the concentration of Na₂WO₄·2H₂O (W) have been investigated and the catalyst prepared with B/P value of 1.5 and W concentration of 5 g L⁻¹ shows the highest activity. The results of kinetic studies show that the catalytic hydrolysis of AB is first order with respect to the catalyst and AB concentrations. By using the quaternary catalyst with a concentration of 0.5 wt % AB, a HG rate of 4.0 L min⁻¹ g⁻¹ is achieved at 30 °C. Moreover, the apparent activation energy for the quaternary catalyst is determined to be 29.0 kJ mol⁻¹, which is comparable to that of noble metal-based catalysts. These results indicate that the Co-W-B-P/Ni is a promising low-cost catalyst for on-board hydrogen generation from hydrolysis of borohydride.     

Hydrogen storage properties of the Mg–Ti–H system prepared by high-energy–high-pressure reactive milling

Magnesium-based alloys are among the promising materials for hydrogen storage and fuel cell applications due to their high hydrogen content. In the present work, we investigated the hydrogen release/uptake properties of the Mg–Ti–H system. Samples were prepared from the mixtures of MgH₂ and TiH₂ in molar ratios of 7:1 and 4:1 using a high-energy-high-pressure (HEHP) mechanical ball-milling method under 13.8 MPa hydrogen pressure. Thermogravimetric analysis (TGA) showed that a relatively large amount of hydrogen (5.91 and 4.82 wt.%, respectively, for the above two samples) was released between 126 and 313 °C while temperature was increased at a heating rate of 5 °C min⁻¹ under an argon flow. The onset dehydrogenation temperature of these mixtures, which is 126 °C, is much lower than that of MgH₂ alone, which is 381 °C. The activation energy of dehydrogenation was 71 kJ mol⁻¹, which is much smaller than that of as-received MgH₂ (153 kJ mol⁻¹) or as-milled MgH₂ (96 kJ mol⁻¹). Furthermore, the hydrogen capacity and the dehydrogenation temperature remained largely unchanged over five dehydrogenation and rehydrogenation cycles.     

Simple and fast fabrication of polymer template-Ru composite as a catalyst for hydrogen generation from alkaline NaBH4 solution

Polymer template-Ru composite (Ru/IR-120) catalyst was prepared using a simple and fast method for generating hydrogen from an aqueous alkaline NaBH₄ solution. The hydrogen generation rate was determined as a function of solution temperature, NaBH₄ concentration, and NaOH (a base-stabilizer) concentration. The maximum hydrogen generation rate reached 132 ml min⁻¹ g⁻¹ catalyst at 298 K, using a Ru/IR-120 catalyst that contained only 1 wt.% Ru. The catalyst exhibits a quick response and good durability during the hydrolysis of alkaline NaBH₄ solution. The activation energy for the hydrogen generation reaction was determined to be 49.72 kJ mol⁻¹.     

A direct measurement of the heat evolved during the sodium and potassium borohydride catalytic hydrolysis

NaBH₄ and KBH₄ hydrolysis reactions (BH₄⁻ + 4H₂O → B(OH)₄⁻ + 4H₂), which can be utilized as a source of high purity hydrogen and be easily controlled catalytically, are exothermic processes. Precise determination of the evolved heat is of outmost importance for the design of the reactor for hydrogen generation. In this work we present an efficient calorimetric method for the direct measurement of the heats evolved during the catalyzed hydrolysis reaction. A modified Setaram Titrys microcalorimeter was used to determine the heat of hydrolysis in a system where water is added to pure solid NaBH₄ or KBH₄ as well as to solid NaBH₄ or KBH₄ mixed with a Co-based solid catalyst. The measured heats of NaBH₄ hydrolysis reaction were: −236 kJ mol⁻¹, −243 kJ mol⁻¹, −235 kJ mol⁻¹, and −236 kJ mol⁻¹, without catalyst and in the presence of Co nanoparticles, CoO and Co₃O₄, respectively. In the case of the KBH₄ hydrolysis reaction, the measured heats were: −220 kJ mol⁻¹, −219 kJ mol⁻¹, −230 kJ mol⁻¹, and −228 kJ mol⁻¹, without catalyst and with Co nanoparticles, CoO and Co₃O₄, respectively. Also, a comparison was made with an aqueous solution of CoCl₂·6H₂O used as catalyst in which case the measured heats were −222 kJ mol⁻¹ and −196 kJ mol⁻¹ for NaBH₄ and KBH₄ hydrolysis, respectively. The influence of solid NaOH or KOH additions on the heat of borohydride hydrolysis has been investigated as well.     

Catalytic dehydrogenation of ammonia borane in non-aqueous medium

Dehydrogenation of Ammonia Borane (NH₃BH₃, AB) catalyzed by transition metal heterogeneous catalysts was carried out in non-aqueous solution at temperatures below the standard polymer electrolyte membrane (PEM) fuel cell operating conditions. The introduction of a catalytic amount (∼2 mol%) of platinum to a solution of AB in 2-methoxyethyl ether (0.02–0.33 M) resulted in a rapid evolution of H₂ gas at room temperature. At 70 °C, the rate of platinum catalyzed hydrogen release from AB was the dehydrogenation rate which was 0.04 g s⁻¹ H₂ kW⁻¹.     

Bio-hydrogen production from acid hydrolyzed wheat starch by photo-fermentation using different Rhodobacter sp

Hydrogen gas production from sugar solution derived from acid hydrolysis of ground wheat starch by photo-fermentation was investigated. Three different pure strains of Rhodobacter sphaeroides (RV, NRLL and DSZM) were used in batch experiments to select the most suitable strain. The ground wheat was hydrolyzed in acid solution at pH = 3 and 90 °C in an autoclave for 15 min. The resulting sugar solution was used for hydrogen production by photo-fermentation after neutralization and nutrient addition. R. sphaeroides RV resulted in the highest cumulative hydrogen gas formation (178 ml), hydrogen yield (1.23 mol H₂ mol⁻¹ glucose) and specific hydrogen production rate (46 ml H₂ g⁻¹ biomass h⁻¹) at 5 g l⁻¹ initial total sugar concentration among the other pure cultures. Effects of initial sugar concentration on photo-fermentation performance were investigated by varying sugar concentration between 2.2 and 13 g l⁻¹ using the pure culture of R. sphaeroides RV. Cumulative hydrogen volume increased from 30 to 232 ml when total sugar concentration was increased from 2.2 to 8.5 g l⁻¹. Further increases in initial sugar concentration resulted in decreases in cumulative hydrogen formation. The highest hydrogen formation rate (3.69 ml h⁻¹) and yield (1.23 mol H₂ mol⁻¹ glucose) were obtained at a sugar concentration of 5 g l⁻¹.     

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.     

Hydrolytic cleavage of ammonia-borane complex for hydrogen production

A new process for generating hydrogen via near room temperature hydrolysis of AB complex using small amounts of platinum group metal catalyst has been studied. Using in situ ¹¹B NMR spectroscopy, the overall rate of K₂Cl₆Pt catalyzed hydrolysis of AB complex was calculated to be third-order. The pre-exponential factor (A) and the activation energy (E_a) of Arrhenius equation, ln k = ln A − E_a/RT, were determined to be: A = 1.6 × 10¹¹ L mol⁻¹ s⁻¹ and E_a = 86.6 kJ mol⁻¹ for temperature range of (25–35 °C). X-ray photoelectron spectroscopy of the residue suggested that the platinum salt was reduced from Pt⁴⁺ to Pt⁰ within the course of the reaction and X-ray diffraction analysis pattern for the residue showed crystallized single-phase boric acid.     

Controllable hydrogen generation by use smart hydrogel reactor containing Ru nano catalyst and magnetic iron nanoparticles

In this study, p(AMPS) hydrogels are synthesized from 2-acrylamido-2-methyl-1-propansulfonic acid (AMPS) via a photo polymerization technique. The hydrogels are used as template for metal nanoparticles and magnetic ferrite nanoparticles, and also as a catalysis vessel in the generation of hydrogen from the hydrolysis of NaBH₄. Approximately 5 nm Ru (0) and 20-30 nm magnetic ferrite particles are generated in situ inside this p(AMPS) hydrogel network and then used as a catalysis medium in hydrogen production by hydrolysis of sodium boron hydride in a basic medium. With an applied external magnetic field, the hydrogel reactor, containing Ru and ferrite magnetic particles, can be removed from the catalysis medium; providing on-demand generation of hydrogen. The effect of various parameters such as the initial concentration of NaBH₄, the amount of catalyst and temperature on the hydrolysis reaction is evaluated. The activation energy for hydrogen production by Ru (0) nanoparticles is found to be 27.5 kJ mol⁻¹; while the activation enthalpy is 30.4 kJ mol⁻¹. The hydrogen generation rate in presence of 5 wt% NaOH and 50 mg p(AMPS)-Ru catalyst is 8.2 L H₂ min⁻¹ g Ru.     

Accurately measuring the hydrogen generation rate for hydrolysis of sodium borohydride on multiwalled carbon nanotubes/Co–B catalysts

Multiwalled carbon nanotubes supported cobalt–boron catalysts (Co–B/MWCNT) were developed via the chemical reduction of aqueous sodium borohydride with cobalt chloride for catalytic hydrolysis of alkaline NaBH₄ solution. The hydrogen generation (HG) rates were measured on an improved high-accuracy, low-cost and automatic HG rate measurement system based on the use of an electronic balance with high accuracy. The HG of Co–B/MWCNT catalyst was investigated as a function of heat treatment, solution temperature, Co–B loading and supporting materials. The catalyst was mesoporous structured and showed lower activation energy of 40.40 kJ mol⁻¹ for the hydrolysis of NaBH₄. The Co–B/MWCNT catalyst was not only highly active to achieve the average HG rate of 5.1 l min⁻¹ g⁻¹ compared to 3.1 l min⁻¹ g⁻¹ on Co–B/C catalyst under the same conditions but also reasonably stable for the continuous hydrolysis of NaBH₄ solution.     

Dehydrogenation characteristics of ammonia borane via boron-based catalysts (Co–B,Ni–B,Cu–B) under different hydrolysis conditions

In the present study, dehydrogenation characteristics of ammonia borane (NH₃BH₃) catalyzed via boron-based catalysts under different hydrolysis conditions were investigated. A series of boron-based catalysts (Co_1−x–B_x, Ni_1−x–B_x, and Cu_1−x–B_x, x: 0.25, 0.50, 0.75) were prepared by sol–gel method. Gels were calcinated at different temperatures (250 °C, 350 °C, and 450 °C) in order to obtain the boron-based catalysts. XRD characterizations revealed that Co–B, Ni–B, and Cu–B crystalline structures were formed during calcination at 450 °C. Hydrogen generation measurements were performed in order to determine the optimum composition of the boron-based catalyst. The maximum hydrogen generation rates were 7607 ml min⁻¹ gcat⁻¹, 3869 ml min⁻¹ gcat⁻¹ and 1178 ml min⁻¹ gcat⁻¹ for Co_0.75B_0.25, Ni_0.75B_0.25 and Cu_0.75B_0.25, respectively. Furthermore, the hydrolysis of NH₃BH₃ was performed at 20 °C, 40 °C, 60 °C and 80 °C under magnetic stirring (750 rpm), ultrasonic irradiation and non-stirring in order to determine how these parameters effect hydrolysis. Activation energies (E_a) were calculated by evaluation of the kinetic data. Under ultrasonic irradiation, the E_a in the presence of Co_0.75B_0.25, Ni_0.75B_0.25 and Cu_0.75B_0.25 were 40.85 kJ mol⁻¹, 43.19 kJ mol⁻¹ and 48.74 kJ mol⁻¹, respectively, which compares favorably with results reported in the literature. Thus, the catalytic activities of the boron-based catalysts were found to be Cu < Ni < Co and the best reaction condition for the catalytic hydrolysis of NH₃BH₃ was determined to be non-stirring < magnetic stirring < ultrasonic irradiation.     

Water-soluble poly(4-styrenesulfonic acid-co-maleic acid) stabilized ruthenium(0) and palladium(0) nanoclusters as highly active catalysts in hydrogen generation from the hydrolysis of ammonia–borane

Water-soluble poly(4-styrenesulfonic acid-co-maleic acid), PSSA-co-MA, stabilized ruthenium(0) and palladium(0) nanoclusters were for the first time prepared in situ from the reduction of ruthenium(III) chloride and potassium tetrachloropalladate(II), respectively, by ammonia–borane during its hydrolysis at room temperature. PSSA-co-MA stabilized ruthenium(0) and palladium(0) nanoclusters having average particle size of 1.9 ± 0.5 and 3.5 ± 1.6 nm, respectively, were isolated from the reaction solution and characterized by TEM and UV–visible electronic absorption spectroscopy. PSSA-co-MA stabilized ruthenium(0) and palladium(0) nanoclusters are highly active catalysts for hydrogen generation from the hydrolysis of ammonia–borane at low temperature. PSSA-co-MA stabilized ruthenium(0) and palladium(0) nanoclusters provide 51,720 and 8720 turnovers, respectively, in the hydrogen generation from the hydrolysis of ammonia–borane at 25 °C before deactivation. Catalytic hydrolysis of ammonia–borane is first order with respect to the catalyst concentration, but zero order with respect to the substrate concentration in the case of both ruthenium(0) and palladium(0) nanoclusters. Activation energies for the hydrolysis of ammonia–borane in the presence of PSSA-co-MA stabilized ruthenium(0) or palladium(0) nanoclusters (54 ± 2 kJ mol⁻¹ and 44 ± 2 kJ mol⁻¹, respectively) are smaller than most of the values reported for the same reaction in the presence of other catalyst systems.     

Characterisation of electrical performance of anode supported micro-tubular solid oxide fuel cell with methane fuel

The reduction and operation of Ni–YSZ anode-supported tubular cells on methane fuel is described. Cells were reduced on pure methane from 650 °C to 850 °C, varying reduction time and methane flow rate. The effect on electrochemical performance with methane fuel was then investigated at 850 °C after which temperature-programmed oxidation (TPO) was employed to measure carbon deposition. Results showed that carbon deposition was minimized after certain reduction conditions. The conclusion was that 30 min reduction at 650 °C with 10 ml min⁻¹ methane reduction flow rate led to the highest current output over 1.2 A cm⁻² at 0.5 V when the cell operated at 850 °C between 10 ml min⁻¹ and 12.5 ml min⁻¹ methane running flow rate. From these results, it is evident that solid oxide fuel cell (SOFC) performance can be substantially improved by optimising preparation, reduction and operating conditions without the need for hydrogen.     

A novel design for a flow field configuration, of a direct methanol fuel cell

We proposed and tested a new and novel arrangement for a direct methanol fuel cell consisting of one inlet for a methanol solution and four outlets for oxidant gas (air), in both the anode and cathode flow fields. It utilizes different operating temperatures of 40 °C and 60 °C, and different methanol solution flow rates of 5 ml min⁻¹, 10 ml min⁻¹, and 20 ml min⁻¹. Test results indicate a significant reduction in produced CO₂ gas in the anode flow channels and product water in the cathode flow channels; consequently, cell performance can be greatly improved. Furthermore, methanol crossover can also be avoided and reduced.     

Biohydrogen production from cornstalk wastes by anaerobic fermentation with activated sludge

An anaerobic fermentation process to produce hydrogen from cornstalk wastes was systematically investigated in this work. Batch experiments numbered series I, II and III were designed to investigate the effects of acid pretreatment, enzymatic hydrolysis (enzymatic temperature, enzymatic time and enzymatic pH) on hydrogen production by using the natural sludge as inoculant. A maximum cumulative H₂ yield of 126.22 ml g⁻¹-CS (Cornstalk, or 146.94 ml g⁻¹-TS, Total Solid) and an average H₂ production rate of 9.58 ml g⁻¹-CS h⁻¹ were obtained from fermentation cornstalk with a concentration of 20 g/L and an initial pH of 7.0 at 36 °C through an optimal pretreatment process. The optimal process was that the substrate was soaked with an HCl concentration of 0.6 wt% at 90 °C for 2 h, and subsequently enzymatic hydrolysis for 72 h at 50 °C and pH 4.8 before fermentation. The biogas consisted of only H₂ and CO₂. In addition, the fermentation system was the typical ethanol-type fermentation according to ethanol and acetate as the main liquid by-products.     

Hydrogen generation from hydrolysis of sodium borohydride using Ni–Ru nanocomposite as catalysts

Magnetic nickel–ruthenium based catalysts on resin beads for hydrogen generation from alkaline NaBH₄ solutions were synthesized with combined methods of chemical reduction and electroless deposition. Factors, such as solution temperature, NaBH₄ loadings, and NaOH concentration, on performance of these catalysts on hydrogen production from alkaline NaBH₄ solutions were investigated. Furthermore, characteristics of these nickel–ruthenium based catalysts were carried out by using various instruments, such as SEM/EDS, XPS, SQUID VSM and BET. These catalysts can be easily recycled from spent NaBH₄ solution with permanent magnets owing to their intrinsic soft ferromagnetism and, therefore, reducing the operation cost of the hydrogen generation process. A rate of hydrogen evolution as high as ca. 400 mL min⁻¹ g⁻¹ could be reached at 35 °C in 10 wt% NaBH₄ solution containing 5 wt% NaOH using Ni–Ru/50WX8 catalysts. Activation energy of hydrogen generation using such catalysts is estimated at 52.73 kJ mol⁻¹.     

A multifactor study of catalyzed hydrolysis of solid NaBH4 on cobalt nanoparticles: Thermodynamics and kinetics

In the present work, hydrogen generation through hydrolysis of a NaBH_4(s)/catalyst_(s) solid mixture was realized for the first time as a solid/liquid compact hydrogen storage system using Co nanoparticles as a model catalyst. The performance of the system was analysed from both the thermodynamic and kinetic points of view and compared with the classical catalyzed hydrolysis of a NaBH₄ solution. The kinetic analysis of the NaBH_4(s)/catalyst_(s)/H₂O_(l) system shows that the reaction is first order with respect to the catalyst concentration, and the activation energy equal to 35 kJ mol_NaBH4⁻¹. Additionally, calorimetric measurements of the heat evolved during the hydrolysis of NaBH₄ solutions evidence the global process energy (−217 kJ mol_NaBH4⁻¹). Characterization of the cobalt nanoparticles before and after the hydrolysis associated with the calorimetric measurements suggests the “in situ” formation of a catalytically active Co_xB phase through “reduction” of an outer protective oxide layer that is regenerated at the end of reaction.     

Hydrogen gas production from acid hydrolyzed wheat starch by combined dark and photo-fermentation with periodic feeding

Hydrogen gas production from acid hydrolyzed waste wheat starch by combined dark and photo-fermentation was investigated in continuous mode with periodic feeding and effluent removal. A mixture of heat treated anaerobic sludge and Rhodobacter sphaeroides (NRRL-B 1727) were used as the seed culture for dark and light fermentations, respectively with biomass ratio of Rhodobacter/sludge = 3. Hydraulic residence time (HRT) was changed between 1 and 8 days by adjusting the feeding periods. Ground waste wheat was acid hydrolyzed at pH = 3 and 121 °C for 30 min using an autoclave and the resulting sugar solution was used as the substrate for combined fermentation after pH adjustment and nutrient addition. The highest daily hydrogen gas production (41 ml d⁻¹), hydrogen yield (470 ml g⁻¹ total sugar = 3.4 mol H₂ mol⁻¹glucose), volumetric and specific hydrogen production rates were obtained at the HRT of 8 days. The highest biomass and the lowest total volatile fatty acids (TVFA) concentrations were also realized at HRT = 8 days indicating VFA fermentation by Rhodobacter sp. at high HRTs. The lowest total sugar loading rate of 0.625 g L⁻¹ d⁻¹ resulted in the highest hydrogen yield and formation rate. Hydrogen gas production by combined fermentation with periodic feeding was proven to be an effective method resulting in high hydrogen yields at long HRTs.     

Influence of multiple oxide (Cr2O3/Nb2O5) addition on the sorption kinetics of MgH2

The influence of multiple additions of two oxides, Cr₂O₃ and Nb₂O₅, as additives on the hydrogen sorption kinetics of MgH₂ after milling was investigated. We found that the desorption kinetics of MgH₂ were improved more by multiple oxide addition than by single addition. Even for the milled MgH₂ micrometric size powders, the high hydrogen capacity with fast kinetics were achieved for the powders after addition of 0.2 mol% Cr₂O₃ + 1 mol% Nb₂O₅. For this composition, the hydride desorbed about 5 wt.% hydrogen within 20 min and absorbed about 6 wt.% in 5 min at 300 °C. Furthermore, the desorption temperature was decreased by 100 °C, compared to MgH₂ without any oxide addition, and the activation energy for the hydrogen desorption was estimated to be about 185 kJ mol⁻¹, while that for MgH₂ without oxide was about 206 kJ mol⁻¹.