Co−O−P composite nanocatalysts for hydrogen generation from the hydrolysis of alkaline sodium borohydride solution

In recent years, catalytic hydrolysis of sodium borohydride is considered to be a promising approach for hydrogen generation towards fuel cell devices, and highly efficient and noble-metal-free catalysts have attracted increasing attention. In our present work, Co₃O₄ nanocubes are synthesized by solvothermal method, and then vapor-phase phosphorization treatment is carried out for the preparation of novel Co−O−P composite nanocatalysts composed of multiple active centers including Co, CoO, and Co₂P. For catalyst characterization, field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), energy dispersive spectrometry (EDS), X-ray diffraction (XRD) and X-ray photoelectric spectroscopy (XPS) are conducted. Optimal conditions for catalyst preparation and application were investigated in detail. At room temperature (25 °C), maximum hydrogen generation rate (HGR) is measured to be 4.85 L min⁻¹ g⁻¹ using a 4 wt% NaBH₄ − 8 wt% NaOH solution, which is much higher than that of conventional catalysts with single component reported in literature. It is found that HGR remarkably increases with the increasing of reaction temperature, and apparent activation energy for catalytic hydrolysis of NaBH₄ is calculated to be 63 kJ mol⁻¹. After reusing for five times, the Co−O−P composite nanocatalysts still retains 78% of the initial activity.     

Superior hydrogen generation from sodium borohydride hydrolysis catalyzed by the bimetallic Co–Ru/C nanocomposite

Sodium borohydride has been widely regarded as a promising hydrogen carrier owing to its greatly hydrogen storing capability (10.8 wt%), high weight density and excellent stability in alkaline solutions. Herein, we first design and synthesize a series of bimetallic M-Ru/C nanocomposites (including Fe–Ru/C, Co–Ru/C, Ni–Ru/C and Cu–Ru/C), via simply alloying of commercial Ru/C with nonprecious metal, for superior H₂ evolution from the NaBH₄ hydrolysis. The result exhibits that H₂ generation is synergetically improved by alloying Ru/C with Co or Ni, while it is hindered by alloying Ru/C with Fe or Cu. Indeed, Co–Ru/C presents the highest efficient catalytic activity for H₂ generation, with the TOF of 117.69 mol(H₂)·mol_Ru^?1·min^?1, whereas Ru/C is only 57.08 mol(H₂)·mol_Ru^?1·min^?1. In addition, the TOF of Co–Ru/C reaches to 436.51 mol(H₂)·mol_Ru^?1·min^?1 (96.7 L(H₂)·g_Ru^?1·min^?1) in the presence of NaOH.     

Novel Ni–Co–B hollow nanospheres promote hydrogen generation from the hydrolysis of sodium borohydride

Ni–Co–B hollow nanospheres were synthesized by the galvanic replacement reaction using a Co–B amorphous alloy and a NiCl₂ solution as the template and additional reagent, respectively. The Ni–Co–B hollow nanospheres that were synthesized in 60 min (Ni–Co–B-60) showed the best catalytic activity at 303 K, with a hydrogen production rate of 6400 mL_hydrogenmin^?1g_catalyst^?1 and activation energy of 33.1 kJ/mol for the NaBH₄ hydrolysis reaction. The high catalytic activity was attributed to the high surface area of the hollow structure and the electronic effect. The transfer of an electron from B to Co resulted in higher electron density at Co sites. It was also found that Ni was dispersed on the Co–B alloy surface as result of the galvanic replacement reaction. This, in turn, facilitated an efficient hydrolysis reaction to enhance the hydrogen production rate. The parameters that influenced the hydrolysis of NaBH₄ over Ni–Co–B hollow nanospheres (e.g., NaOH concentration, reaction temperature, and catalyst loading) were investigated. The reusability test results show that the catalyst is active, even after the fifth run. Thus, the Ni–Co–B hollow nanospheres are a practical material for the generation of hydrogen from chemical hydrides.     

Graphene supported bimetallic G–Co–Pt nanohybrid catalyst for enhanced and cost effective hydrogen generation

A highly active and stable bimetallic nano-hybrid catalyst Graphene–Cobalt–Platinum (G–Co–Pt) is proposed for the enhanced and cost effective generation of hydrogen from Sodium Borohydride. Three different nano-hybrid catalysts namely Graphene–Cobalt (G–Co), Graphene–Platinum (G–Pt) and Graphene–Cobalt–Platinum (G–Co–Pt) are synthesized, characterized using XRD, FTIR, SEM, HRTEM, EDAX and Cyclic voltammetry (CV) analysis and tested for hydrogen generation. The activity and stability of the catalysts are analyzed by estimating the turnover frequency (TOF), the electrochemically active surface area (ECSA), the percentage decay of current density over ten cycles of CV and the decay in the rate of hydrogen generation with the age of catalyst. Among the three catalysts G–Co–Pt exhibits the highest catalytic activity (TOF = 107 min⁻¹, ECSA = 75.32 m²/gm) and stability. The evaluated value of activation energy of the catalytic hydrolysis using G–Co–Pt is 16 ± 2 kJ mol⁻¹.     

Polypyrrole supported Co–W–B nanoparticles as an efficient catalyst for improved hydrogen generation from hydrolysis of sodium borohydride

Effective and reusable catalysts with high performance are essentially necessary for NaBH₄ based on-demand hydrogen generators to the widespread use for energy conversion in fuel cell power systems. Herein, we report a facile synthesis of surfactant-directed polypyrrole-supported Co–W–B nanoparticles as a robust catalyst for efficient hydrolysis of NaBH₄ reaction. This non-noble metal catalyst provides much higher catalytic activity than a conventional cobalt boride catalyst. By incorporating tungsten to catalyst composition and tuning molar ratio of W/(Co + W), about a four-fold higher hydrogen generation rate was attained compared to bare Co–B. Among the all catalysts tested, Co–W–B/PPy with 7.5% W possessed the remarkable catalytic performance of 9.92 L min^?1 g^?1 and high stability over five cycles with the apparent activation energy of 49.18 kJ mol^?1.     

CdO–CdS nanocomposites with enhanced photocatalytic activity for hydrogen generation from water

Nanocomposites of CdO–CdS have been prepared in ethylene glycol water mixture followed by heating at 300 °C. TEM and XRD studies confirmed the atomic scale mixing of CdO and CdS nanoparticles, leading to the formation of CdSO₃ phase at the interfacial region between CdO and CdS. Photocatalytic studies for hydrogen generation from water show an enhanced activity for CdO–CdS composites compared to individual components namely CdO or CdS nanoparticles. Based on optical absorption, surface area measurements, steady state and time resolved fluorescence studies, it is established that, enhanced absorption in the visible region, higher surface area and increase in lifetime of the charge carriers are responsible for the observed increase in hydrogen yield from water when composite sample was used as the photocatalyst compared to individual components. The composite sample when combined with Pt as co-catalyst exhibit a large increase in the photocatalytic activity.     

High-performance cobalt–tungsten–boron catalyst supported on Ni foam for hydrogen generation from alkaline sodium borohydride solution

Low cost and catalytically effective transition metal catalysts are highly wanted in developing on-demand hydrogen generation system for practical onboard application. By using a modified electroless plating method, we have prepared a robust Co–W–B amorphous catalyst supported on Ni foam (Co–W–B/Ni foam catalyst) that is highly effective for catalyzing hydrogen generation from alkaline NaBH₄ solution. It was found that the plating times, calcination temperature, NaBH₄ and NaOH concentrations all exert considerable influence on the catalytic effectiveness of Co–W–B/Ni foam catalyst towards the hydrolysis reaction of NaBH₄. Via optimizing these preparation and reaction conditions, a hydrogen generation rate of 15 L/min g (Co–W–B) has been achieved, which is comparable to the highest level of noble metal catalyst. In consistent with the observed pronounced catalytic activity, the activation energy of the hydrolysis reaction using Co–W–B/Ni foam catalyst was determined to be only 29 kJ/mol. Based on the phase analysis and structural characterization results, the mechanism underlying the observed dependence of catalytic effectiveness on the calcination temperature was discussed.     

Mesoporous Co–B nanocatalyst for efficient hydrogen production by hydrolysis of sodium borohydride

Two types of mesoporous Co–B nanocatalysts were prepared by the reduction of cobalt chloride with Sodium Borohydride (SBH) in the presence of cationic and non-ionic surfactant templates, namely n-cetyl-trimethyl-ammonium bromide (CTAB) and Pluronic (P123) respectively. Nitrogen adsorption–desorption isotherms revealed the presence of slit-like pores on the catalyst surface which provide high effective surface area. These surface enhanced catalysts were tested for hydrogen production by hydrolysis of sodium borohydride. The mesoporous Co–B catalysts showed much higher activity (4 times) in comparison to the non-porous Co–B, which can be attributed to the higher surface area of the mesoporous structures. Co–B/P123 catalyst showed the highest hydrogen generation rate owing to the presence of wide uniform pores which facilitated easier interaction of the reactants to release hydrogen. The lack of stability in the pore structure is observed at elevated temperatures for both the mesoporous Co–B catalyst.     

Amorphous cobalt–boron/nickel foam as an effective catalyst for hydrogen generation from alkaline sodium borohydride solution

Low cost and catalytically effective transition metal catalysts are of interest for the development of on-board hydrogen generation systems for fuel-cell vehicles. In the present study a modified electroless plating method was developed for the preparation of amorphous Co–B catalyst supported on Ni foam. Compared to the conventional electroless plating method, the newly developed method is more effective and produces Co–B catalyst with much higher catalytic activity. The catalytic activity of the supported Co–B catalyst was found to be highly dependent on the plating times and calcination conditions. Through optimization of these preparation conditions we were able to prepare a catalyst capable of a hydrogen generation rate of 11 l (min g)⁻¹ (catalyst) in a 20 wt.% NaBH₄ + 10 wt.% NaOH solution. Preliminary phase analyses and microstructure characterization were performed to understand the effects of preparation conditions on the catalytic activity of the Co–B catalyst.     

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.     

Ni–B and Zr–Ni–B in-situ catalytic performance for hydrogen generation from sodium borohydride,ammonia borane and their mixtures

In this study, the parameters on the catalytic hydrolysis of the sodium borohydride (NaBH4, SBH) and ammonia boranes (NH3BH3, AB) mixtures were investigated such as the effect of Zr additive in the catalyst, using in-situ or powder catalysts, the molar ratio of the SBH/AB mixture (2, 4, 8, neat SBH, neat AB) and temperature. As the catalyst, in-situ synthesized Ni–B and Zr–Ni–B for the first time were used to produce H₂ from hydrolysis of the SBH and AB mixtures. The SBH and AB mixtures were used to determine provided or not an effect on reaction. Catalyst preparation and hydrolysis reactions took place in the same reactor spontaneously for in-situ works. The Zr–Ni–B catalyst gives better results than Ni–B and increases efficiency at 25 °C and 35 °C temperature. When Zr–Ni–B catalyst compared experimentally among themselves, the best yield result at 45 °C temperature, for neat SBH, mole ratio in 4 and mole ratio in 8, as 87%, 86% and 83% respectively. For hydrolysis reactions with Zr–Ni–B catalyst, activation energies of SBH and AB were calculated as 45.23 kJ/mol and 79.76 kJ/mol, respectively. SEM, BET, XPS analyzes have been used to characterize these catalysts. The addition of Zr provided increase effect on the surface area. The surface area increases from 44.33 m²/g to 175.50 m²/g.     

Sodium borohydride and propylene glycol,an effective combination for the generation of 2.3 wt% of hydrogen

Sodium borohydride NaBH₄ (SB) readily and completely reacts with four equivalents of propylene glycol HOCH₂CH(OH)CH₃ (PG), resulting in the liberation of four equivalents of H₂ at temperatures starting from 25 °C. Alcoholysis (or glycolysis) takes place. The system SB-4PG is then an attractive H₂ generator thanks to an effective gravimetric hydrogen storage capacity of 2.3 wt%. It offers several other advantages: there is no need of catalyst; there is no precipitation of by-product; PG is among the safest alcohols (much safer than e.g. methanol). The potential of SB-4PG as H₂ generator is thus illustrated and discussed herein.     

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.     

Fast and effective hydrogen production from ethanolysis and hydrolysis reactions of potassium borohydride using phosphoric acid

The hydrogen production from potassium borohydride (KBH₄) with the ethanolysis and hydrolysis reactions using the phosphoric acid as a catalyst is performed for the first time. KBH₄ concentration, phosphoric acid concentration and temperature effects were investigated for the optimum hydrogen production from ethanolysis and hydrolysis reactions of KBH₄. The maximum hydrogen production rates in the ethanolysis and hydrolysis reactions with 1 M phosphoric acid are 6423 and 4296 ml min^?1g^?1, respectively. At the same time, the ethanolysis and hydrolysis reactions with the 1 M acid concentration were completed within 7 and 9 s, respectively. The total conversions obtained for the volume ratio of KBH₄/acid of (1:1) were 100%. The power law kinetic model is performed for the kinetic studies. The activation energies for the ethanolysis and hydrolysis reactions of KBH₄ using phosphoric acid are found as 2.98 and 2.60 kJ mol^?1.     

Graphene modified Co–B catalysts for rapid hydrogen production from NaBH4 hydrolysis

Graphene oxide (GO) modified Co–B catalysts for NaBH₄ hydrolysis have been synthesized by the chemical reduction in this work. The structural features and catalytic performance of as-prepared samples have been investigated and discussed as a function of amounts of GO. According to structure characterization, the catalysts still retain the amorphous structure of Co–B alloy with the addition of GO, while GO exists as reduced GO (r-GO). The textural analysis and morphology observation indicate that the appropriate amount of GO in Co–B catalyst results in the obvious increase of specific surface area and uniform clustered morphology, which contributes to improve active surface area for catalytic reactions. The results of surface species characterization show that the electron density at active Co sites increases due to an electron transfer from B to Co facilitated by r-GO. It has been found that 50 mg GO modified Co–B catalyst exhibits especially high activity with a hydrogen generation rate of 14.34 L min⁻¹·g_catalyst⁻¹ and much lower activation energy of 26.2 kJ mol⁻¹ for hydrolysis reaction of NaBH₄. Meanwhile, the reusability evaluations show that the catalyst preserves high stability which can still maintain 81.5% of its initial activity after 5 catalytic cycles.     

Hydrogen generation from hydrolysis of sodium borohydride by cubic Co–La–Zr–B nano particles as novel catalyst

Cubic Co–La–Zr–B nano particles were prepared in situ for the first time from the reduction of Co(II), La(III) and Zr(IV) chloride by sodium borohydride in methanol under reflux condition. Poly N-vinyl-2-pyrrolidone (PVP) as stabilizing agent was used for preparation of Co–La–Zr–B nano particles. Obtained powders were characterized by XRD, BET, ICP, SEM, TEM and UV–vis techniques. XRD patterns declare that under argon atmosphere only metalboride phase has been crystallized and it was not seen any oxide phase of metals. TEM image depicts that PVP stabilized nano particles are square shaped particles that containing many nanoclusters. Cubic Co–La–Zr–B nano particles were also confirmed by SEM image. Co–La–Zr–B is highly active catalysts for hydrogen generation from the hydrolysis of sodium borohydride. 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 = 53 kJ mol⁻¹) and effects of the catalyst dosage, amount of NaBH₄, and temperature on the rate of the catalytic hydrolysis of sodium borohydride. Catalytic hydrolysis of NaBH₄ is first order with respect to the catalyst concentration and also first order to the NaBH₄ concentration in the case of cubic Co–La–Zr–B nano particles.     

Nanocatalyst: Electrospun nanofibers of PVDF – Dicationic tetrachloronickelate (II) anion and their effect on hydrogen generation from the hydrolysis of sodium borohydride

In this article, we report poly(vinylidene fluoride) (PVDF) – dicationic tetrachloronickelate (II) anion (dicationic ionic salt [C₆(mpy)₂][NiCl₄]²⁻) nanofiber composites used as catalyst for hydrogen generation from the hydrolysis of sodium borohydride. The nanofiber composites were produced by electrospinning method. The synthesized nanofibers are characterized by SEM, TEM, EDX, and FTIR. The rate of hydrogen generation from catalyzed hydrolysis of NaBH₄ solution was determined as a function of temperature, substrate concentration, and catalyst concentration in the presence of prepared catalyst. The result shows that IL based nanofiber composite is a highly efficient and most important advantage that it can be easily recovered and repeatedly reused.     

Highly-dispersed surfactant-free bimetallic Ni–Pt nanoparticles as high-performance catalyst for hydrogen generation from hydrous hydrazine

Highly-dispersed surfactant-free bimetallic Ni–Pt nanoparticles (NPs) with a particle size as small as 2.4 nm were successfully synthesized using NaBH₄ as reducing agent in the presence of NaOH, which exhibit excellent catalytic performance with very fast kinetics for selective decomposition of hydrous hydrazine to hydrogen at room temperature. NaOH plays an important role in the formation of highly-dispersed Ni–Pt nanoparticles. The present results bring light to new opportunities in the development of high-performance metal nanoparticle catalysts and encourage the effective application of hydrous hydrazine as a promising hydrogen storage material.     

Chitosan-mediated Co–Ce–B nanoparticles for catalyzing the hydrolysis of sodium borohydride

Highly dispersed Co–Ce–B nanoparticles supported on chitosan-derived carbon (Co–Ce–B/Chi–C) were synthesized through chemical reduction and carbonization. The morphology and microstructure of the Co–Ce–B/Chi–C nanocomposite were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Brunauer–Emmett–Teller adsorption analysis. This nanocomposite had uniform morphology and large surface area, and it showed high catalytic activity for NaBH₄ hydrolysis and good cycle stability. Compared with unsupported Co–Ce–B particles, this nanocomposite showed greatly increased catalytic activity for NaBH₄ hydrolysis. A remarkably high hydrogen generation rate of 4760 mL^?1 min^?1 g^?1 at 30 °C was achieved with low activation energy of 33.1 kJ mol^?1. These results indicate that the Co–Ce–B/Chi–C nanocomposite is a promising catalyst for on-demand hydrogen generation via NaBH₄ hydrolysis.