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.     

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.     

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.     

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.     

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.     

Electroless-deposited Co–P catalysts for hydrogen generation from alkaline NaBH4 solution

Cobalt–phosphorus (Co–P) catalysts, which were electroless deposited on Cu sheet, have been investigated for hydrogen generation from alkaline NaBH₄ solution. The microstructures of the as-prepared Co–P catalysts and their catalytic activities for hydrolysis of NaBH₄ are analyzed in relation to pH value, NaH₂PO₂ concentration, and the deposition time. Experimental results show that the Co–P catalyst formed in the bath solution with pH value of 12.5, NaH₂PO₂ concentration of 0.8 M, and the deposition time no more than 6 min presents the highest hydrogen generation rate of 1846 mL min⁻¹ g⁻¹. Furthermore, the as-prepared catalyst also shows good cycling capability and the corresponding activation energy is calculated to be 48.1 kJ mol⁻¹. The favorable catalytic performance of the electroless-deposited Co–P catalysts indicates their potential application for quick hydrogen generation from hydrolysis of NaBH₄ solution.     

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.     

Catalytic hydrolysis of sodium borohydride by a novel nickel–cobalt–boride catalyst

With the aim of designing an efficient hydrogen generator for portable fuel cell applications nickel–cobalt–boride (Ni–Co–B) catalysts were prepared by a chemical reduction method and their catalytic hydrolysis reaction with alkaline NaBH₄ solution was studied. The performance of the catalysts prepared from NaBH₄ solution with NaOH, and without NaOH show different hydrogen generation kinetics. The rate of hydrogen generation was measured using Ni–Co–B catalyst as a function of the concentrations of NaOH and NaBH₄, as well as the reaction temperature, in the hydrolysis of alkaline NaBH₄ solution. The hydrogen generation rate increases for lower NaOH concentrations in the alkaline NaBH₄ solution and decreases after reaching a maximum at 15 wt.% of NaOH. The hydrogen generation rate is found to be constant with respect to the concentration of NaBH₄ in the alkaline NaBH₄ solution. The activation energy for hydrogen generation is found to be 62 kJ mol⁻¹, which is comparable with that of hydrogen generation by a ruthenium catalyst.     

Hydrogel assisted nickel nanoparticle synthesis and their use in hydrogen production from sodium boron hydride

In this study, hydrogels were synthesized from 2-acrylamido-2-methyl-1-propansulfonic acid (AMPS) via a photo polymerization technique. Approximately 100 nm Ni metal nanoparticles were generated in situ inside these p(AMPS) hydrogel networks and used as a catalyst in hydrogen production by hydrolysis of sodium boron hydride in a basic medium. The effects of several parameters on the hydrolysis reaction such as the amount of catalyst, the initial concentration of NaBH₄, and the temperature were investigated. The activation energy, activation enthalpy and activation of entropy for the reaction were calculated as 42.28 kJ mol⁻¹, 39.59 kJ mol⁻¹ and −171.67 J mol⁻¹ K⁻¹, respectively.     

Hydrogen generation by hydrolysis of NaBH4 with efficient Co–P–B catalyst: A kinetic study

Amorphous catalyst alloy powders in form of Co–P, Co–B, and Co–P–B have been synthesized by chemical reduction of cobalt salt at room temperature for catalytic hydrolysis of NaBH₄. Co–P–B amorphous powder showed higher efficiency as a catalyst for hydrogen production as compared to Co–B and Co–P. The enhanced activity obtained with Co–P–B (B/P molar ratio = 2.5) powder catalyst can be attributed to: large active surface area, amorphous short range structure, and synergic effects caused by B and P atoms in the catalyst. The roles of metalloids (B and P) in Co–P–B catalyst have been investigated by regulating the B/P molar ratio in the starting material. Heat-treatment at 773 K in Ar atmosphere causes the decrease in hydrogen generation rate due to partial Co crystallization in Co–P–B powder. Kinetic studies on the hydrolysis reaction of NaBH₄ with Co–P–B catalyst reveal that the concentrations of both NaOH and catalyst have positive effects on hydrogen generation rate. Zero order reaction kinetics is observed with respect to NaBH₄ concentration with high hydride/catalyst molar ratio while first order reaction kinetics is observed at low hydride/catalyst molar ratio. Synergetic effects of B and P atoms in Co–P–B catalyst lowers the activation energy (32 kJ mol⁻¹) for hydrolysis of NaBH₄. The stability, reusability, and durability of Co–P–B catalyst have also been investigated and reported in this work. It has been found that by using B/P molar ratio of 2.5 in Co–P–B catalyst, highest H₂ generation rate of about ∼4000 ml min⁻¹ g⁻¹ can be achieved. This can generate 720 W for Proton Exchange Membrane Fuel Cells (0.7 V): which is necessary for portable devices.     

Chemical kinetics of Ru-catalyzed ammonia borane hydrolysis

Ammonia borane (AB) is a candidate material for on-board hydrogen storage, and hydrolysis is one of the potential processes by which the hydrogen may be released. This paper presents hydrogen generation measurements from the hydrolysis of dilute AB aqueous solutions catalyzed by ruthenium supported on carbon. Reaction kinetics necessary for the design of hydrolysis reactors were derived from the measurements. The hydrolysis had reaction orders greater than zero but less than unity in the temperature range from 16 °C to 55 °C. A Langmuir–Hinshelwood kinetic model was adopted to interpret the data with parameters determined by a non-linear conjugate-gradient minimization algorithm. The ruthenium-catalyzed AB hydrolysis was found to have activation energy of 76 ± 0.1 kJ mol⁻¹ and adsorption energy of −42.3 ± 0.33 kJ mol⁻¹. The observed hydrogen release rates were 843 ml H₂ min⁻¹ (g catalyst)⁻¹ and 8327 ml H₂ min⁻¹ (g catalyst)⁻¹ at 25 °C and 55 °C, respectively. The hydrogen release from AB catalyzed by ruthenium supported on carbon is significantly faster than that catalyzed by cobalt supported on alumina. Finally, the kinetic rate of hydrogen release by AB hydrolysis is much faster than that of hydrogen release by base-stabilized sodium borohydride hydrolysis.     

Hydrogen generation from catalytic hydrolysis of alkaline sodium borohydride solution using attapulgite clay-supported Co-B catalyst

An attapulgite clay-supported cobalt-boride (Co-B) catalyst used in portable fuel cell fields is prepared in this paper by impregnation-chemical reduction method. The cost of attapulgite clay is much lower compared with some other inert carriers, such as activated carbon and carbon nanotube. Its microstructure and catalytic activity are analyzed in this paper. The effects of NaOH concentration, NaBH₄ concentration, reacting temperature, catalyst loadings and recycle times on the performance of the catalysts in hydrogen production from alkaline NaBH₄ solutions are investigated. Furthermore, characteristics of these catalysts are carried out in SEM, XRD and TEM analysis. The high catalytic activity of the catalyst indicates that it is a promising and practical catalyst. Activation energy of hydrogen generation using such catalysts is estimated to be 56.32 kJ mol⁻¹. In the cycle test, from the 1st cycle to the 9th cycle, the average hydrogen generation rate decreases gradually from 1.27 l min⁻¹ g⁻¹ Co-B to 0.87 l min⁻¹ g⁻¹ Co-B.     

Metal-Schiff Base complex catalyst in KBH4 hydrolysis reaction for hydrogen production

It is the first study to synthesize Co(II)-Schiff Base complex and to use it like a catalyst for potassium borohydride hydrolysis reaction to hydrogen production. Co(II)-complex is synthesized with CoCl₂·6H₂O and 5-Amino-2,4-dichlorophenol-3,5-di-tert-butylsalisylaldimine ligand. KBH₄ hydrolysis reaction is studied according as percentage of KBH₄, percentage of KOH, amount of Co-Schiff Base complex catalyst and temperature effects. Co-Schiff Base complex is highly effective catalyst and initial rates (R_o) of KBH₄ hydrolysis reaction were 61220.00 and 99746.67 mL H₂. g⁻¹ cat. min⁻¹ at 30 °C and 50 °C. Furthermore this study includes the kinetic calculations and for this reaction calculated activation energy is 17.56 kJ mol⁻¹.     

Synthesis of cobalt-doped catalyst for NaBH4 hydrolysis using eggshell biowaste

In the present study, a cobalt-doped catalyst was prepared from chicken eggshell powder (CEP) biowaste to be used in the hydrolysis of sodium borohydride (NaBH₄). In the presence of the prepared catalyst (CEP_cat), possible effects of the parameters of NaOH concentration (%), catalyst amount (g), NaBH₄ concentration (%), process temperature (^oC) and reusability affecting the hydrolysis of sodium borohydride were examined. The CEP_cat obtained was characterized with FT-IR, TGA, XRD, SEM and EDX analyses. The hydrogen generation rate (HGR) was determined as 432 mL g_Co⁻¹ min⁻¹ in the presence of 1 g CEP_cat, a CoO/CaO ratio of 10/90 and 1% NaBH₄ concentration. The activation energy of the NaBH₄ hydrolysis reaction was calculated as 16.78 kJ mol⁻¹. After 16 reuses of the CEP_cat there was no significant decrease in the hydrogen volume. Compared to the first use while there was an increase in the HGR. These results showed that the CEP_cat prepared has a significant advantage over other catalysts for use in NaBH₄ hydrolysis.     

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.     

An effective synthesis route for improving the catalytic activity of carbon-supported Co–B catalyst for hydrogen generation through hydrolysis of NaBH4

A novel method for synthesis of carbon-supported cobalt boride catalyst was developed for hydrogen generation from catalytic hydrolysis of NaBH₄ solution. The activated carbon and carbon black supported catalysts prepared by “reduction–precipitation” method were found to be much more active than those prepared by conventional “impregnation–reduction” method inspite of the same Co content. A maximum hydrogen generation was achieved using carbon black supported Co–B, which lowers the activation energy to 56.7 kJ mol⁻¹. The effects of NaOH concentration (1–15 wt.%), NaBH₄ concentration (5–20 wt.%) and reaction temperature (25–40 °C) on the performance of the most active catalyst (Co–B/C_B) were investigated in detail. The results indicated that this catalyst can be used in a hydrogen generator for mobile applications such as PEMFC systems due to its high catalytic activity and simple preparation method.     

Low Pt content on the Pd45Pt5Sn50 cathode catalyst for PEM fuel cells

Pd₄₅Pt₅Sn₅₀ electrocatalyst was prepared by a NaBH₄ reduction of PdCl₂, H₂PtCl₆ and SnCl₂ in THF at 0 °C. This catalyst was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS) microanalysis and hydrodynamic electrochemical technique. XRD, SEM and TEM results demonstrate that the borohydrate reduction methodology enable the synthesis of conglomerated particles nanometric in size ranging from 1 to 6 nm. Oxygen reduction reaction (ORR) activity was investigated on carbon dispersed catalyst by rotating disk electrode (RDE) technique in H₂SO₄ 0.5 M. The effect of temperature on the kinetics was analyzing resulting in an apparent activation energy of 42.54 ± 1 kJ mol⁻¹, value which is less than the obtained for the nanostructured bimetallic PdSn electrocatalyst under the same experimental condition. The Pd₄₅Pt₅Sn₅₀ electrocatalyst dispersed on a carbon powder was tested as cathode electrocatalyst in a membrane-electrode assembly (MEA) arriving to a power density of 210 mW cm⁻² at 0.35 V and 80 °C.     

Effect of various Co–B catalyst synthesis conditions on catalyst surface morphology and NaBH4 hydrolysis reaction kinetic parameters

The objective of this work is to study the effect of various Co–B catalyst synthesis conditions on the catalyst surface morphology and kinetic parameters. The Co–B catalyst was synthesized on IR-120/TP-207 resin surface by using ion exchange and chemical reduction method using NaBH₄ as a reduction agent. The reduction conditions which were investigated here were: reduction temperature, NaBH₄ concentration, pH value, NaBH₄ adding flowrate and different types of resins. The result shows reduction temperature gives the most dramatic effect on surface morphology which is caused by competing reactions of reduction and hydrolysis. Low reduction temperature resulted in a slower Co–B reduction rate and made the catalyst surface denser with a branched structure. This created more surface area than higher reduction temperatures. Low reduction temperature catalyst had the better performance on NaBH₄ hydrolysis reaction for hydrogen generation rate. The optimal reduction temperature of the Co–B/IR-120 is 25 °C. The L-H model was used to regress kinetic parameters from the experiment data. The frequency factor, activation energy and adsorption constant are 1.17 × 10⁹ mol gcat⁻¹ min⁻¹, 70.65 kJ mol⁻¹, and 6.8 L mol⁻¹ at 40 °C, respectively. Finally, the TP-207 resin was used instead of IR-120. After scanning for all catalyst synthesis conditions, the Co–B/TP-207 had the higher catalyst loading, faster hydrogen generation rate and more stable than Co–B/IR-120.     

Study on reversible hydrogen sorption behaviors of a 3NaBH4/HoF3 composite

In this work, the complex hydrogen sorption behaviors in a 3NaBH₄/HoF₃ composite prepared through mechanical milling were carefully investigated, including the reactions occurred during ball milling and de-/rehydrogenation processes. Different from other rear earth fluorides, the HoF₃ can react with NaBH₄ during ball milling, leading to the formations of Na–Ho–F and Na–Ho–BH₄ complex compounds. The first dehydriding of the 3NaBH₄/HoF₃ composite can be divided into 4 steps, including the ion exchange between H⁻ and F⁻, the formation of NaHo(BH₄)₄, the decomposition of NaHo(BH₄)₄ and reaction of NaBH₄ with Na–Ho–F compounds. The final products, HoB₄, HoH₃ and NaF, can be rehydrogenated to generate NaBH₄ and NaHoF₄ with an absorption capacity of 2.3 wt% obtained at 400 °C. Based on the Pressure–Composition–Temperature measurements, the de-/rehydrogenation enthalpies of the 3NaBH₄/HoF₃ composite are determined to be 88.3 kJ mol⁻¹ H₂ and −27.1 kJ mol⁻¹ H₂, respectively.     

Hydrogen generation from catalytic hydrolysis of sodium borohydride solution using Cobalt–Copper–Boride (Co–Cu–B) catalysts

Co–Cu–B, as a catalyst toward hydrolysis of sodium borohydride solution, has been prepared through chemical reduction of metal salts, CoCl₂·6H₂O and CuCl₂, by an alkaline solution composed of 7.5wt% NaBH₄ and 7.5wt% NaOH. The effects of Co/Cu molar ratio, calcination temperature, NaOH and NaBH₄ concentration and reaction temperature on catalytic activity of Co–Cu–B for hydrogen generation from alkaline NaBH₄ solution have been studied. X-ray diffraction (XRD), scanning electron microscope (SEM) and Nitrogen adsorption–desorption isotherm have been employed to understand the results. The Co–Cu–B catalyst with a Co/Cu molar ratio of 3:1 and calcinated at 400 °C showed the best catalytic activity at ambient temperature. The activation energy of this catalytic reaction is calculated to be 49.6 kJ mol⁻¹.