Methanolysis of ammonia borane catalyzed by magnetically isolable RHODIUM(0) nanoparticles

This article reports the preparation and employment of rhodium (0) nanoparticles (Rh⁰NPs) on the surface of magnetite nanospheres, denoted as Rh⁰@Fe₃O₄, as magnetically isolable nanocatalyst in the methanolysis of ammonia borane (MAB). The monodispersed Fe₃O₄ nanospheres are fabricated by a simple technique and used as nanosupport for Rh⁰NPs which are well stabilized and homogeneously distributed on the surface of nanospheres with a mean particle size of 2.8 ± 0.5 nm. The as-synthesized Rh⁰@Fe₃O₄ has a remarkable TOF value of 184 min⁻¹ in the MAB to produce H₂ gas in RT. Most of all, Rh⁰@Fe₃O₄ nanocatalyst can be reused, evolving 3.0 mol of H₂ gas for a mole of AB, keeping 100% of its initial activity even in the fourth reuse of MAB at 25 °C. Recovery of the Rh⁰@Fe₃O₄ nanocatalyst can be accomplished by simply approaching an external magnet, which eliminates many laborious catalyst removal steps in catalytic reactions. Reported are the outcomes of kinetic investigation, done by altering the concentration of substrate and catalyst together with temperature. Kinetic studies reveal that the catalytic MAB shows dependence on the concentration of reactants and temperature.     

Oxygen reduction reaction and hydrogen evolution reaction catalyzed by carbon-supported molybdenum-coated palladium nanocubes

Oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) are two important processes for electrochemical energy storage and conversion. Herein, we describe the preparation of carbon-supported Pd nanocubes@Mo core@shell nanostructures as efficient dual catalysts for both ORR and HER. The core@shell structure was manifested by high-resolution transmission electron microscopy measurements, including high angle-angular dark field-scanning transmission electron microscopy and elemental mapping analysis. Further structural insights were obtained in X-ray diffraction and X-ray photoelectron spectroscopy measurements. The nanostructures exhibited apparent electrocatalytic activity toward both ORR and HER, and the performances were markedly higher than those without the deposition of a Mo overlayer. In ORR, the activity was even better than that of commercial Pt/C within the context of onset potential, specific and mass activities; whereas in HER, the performance of Pd nanocubes@Mo core@shell nanostructures remained subpar as compared to that of Pt/C in terms of the overpotential to reach the current density of 10 mA cm^?2, the Tafel slope was comparable and the stability was excellent. The excellent electrocatalytic performance can be attributed to the Pd-Mo synergistic effects imparted from the core-shell structure.     

Ruthenium(0) nanoparticles supported on nanotitania as highly active and reusable catalyst in hydrogen generation from the hydrolysis of ammonia borane

Ruthenium(0) nanoparticles supported on the surface of titania nanospheres (Ru(0)/TiO₂) were in situ generated from the reduction of ruthenium(III) ions impregnated on nanotitania during the hydrolysis of ammonia borane. They were isolated from the reaction solution by centrifugation and characterized by a combination of advanced analytical techniques. The results reveal that highly dispersed ruthenium(0) nanoparticles of size in the range 1.5–3.3 nm were formed on the surface of titania nanospheres. Ru(0)/TiO₂ show high catalytic activity in hydrogen generation from the hydrolysis of ammonia borane with a turnover frequency value up to 241 min⁻¹ at 25.0 ± 0.1 °C. They provide unprecedented catalytic lifetime measured by total turnover number (TTO = 71,500) in hydrogen generation from the hydrolysis of ammonia borane at 25.0 ± 0.1 °C. The report also includes the results of kinetic study on the catalytic hydrolysis of ammonia borane depending on the temperature to determine the activation energy of the reaction (E_a = 70 ± 2 kJ/mol) and the catalyst concentration to establish the rate law of the reaction.     

Pd nanoparticles anchoring to core-shell Fe3O4@SiO2-porous carbon catalysts for ammonia borane hydrolysis

A modified Stöber method is applied to synthesize the magnetic core-shell Fe₃O₄@SiO₂ particles, followed by compositing a series of porous glucose-derived carbon with ZnCl₂ as etchant. Then, ultrafine Pd nanoparticles (NPs) are successfully anchored to the resulting Fe₃O₄@SiO₂-PC composites with an in-situ reduction strategy. The particle sizes of Pd NPs are mainly centered in the range of 2.3–4.3 nm in the as-prepared Pd/Fe₃O₄@SiO₂-PC catalysts, owning a hierarchical porous structure with high specific surface area (S_BET = 626.0 m² g⁻¹) and large pore volume (V_p = 0.61 cm³ g⁻¹). Their catalytic behavior for the hydrogen generation from ammonia borane (AB) hydrolysis is investigated in details. The corresponding apparent activation energy is as low as 28.4 kJ mol⁻¹ and the reaction orders with AB and Pd concentrations are near zero and 1.10 under the present conditions, respectively. In addition, the magnetic catalysts, which could be easily separated out by a magnet, are still highly active even after nine runs, revealing their excellent reusability.     

Hydrogen generation from the hydrolysis of hydrazine-borane catalyzed by rhodium(0) nanoparticles supported on hydroxyapatite

Herein, we report the preparation and characterization of rhodium(0) nanoparticles supported on hydroxyapatite (Ca₁₀(OH)₂(PO₄)₆, HAP) and their catalytic use in the hydrolysis of hydrazine-borane, which attracts recent attention as promising hydrogen storage materials. Hydroxyapatite supported rhodium(0) nanoparticles were readily prepared by the hydrazine-borane reduction of rhodium(III)-exchanged hydroxyapatite in situ during the hydrolysis of hydrazine-borane at room temperature. Characterization of the resulting material by ICP–OES, TEM, SEM, EDX, XRD, XPS spectroscopies and N₂ adsorption–desorption technique, which shows the formation of rhodium(0) nanoparticles well dispersed on hydroxyapatite support. The catalytic performance of these new supported rhodium(0) nanoparticles in terms of activity, lifetime and reusability was tested in the hydrolysis of hydrazine-borane. They were found to be highly active, long-lived and reusable catalyst in this important catalytic reaction even at low temperatures and high initial [substrate]/[catalyst] conditions. This report also includes the detailed kinetic study of the hydrolysis of hydrazine-borane catalyzed by hydroxyapatite supported rhodium(0) nanoparticles depending on the catalyst concentration, substrate concentration, and temperature.     

Hydrogen generation from NaBH4 hydrolysis catalyzed by cobalt (0)-Deposited cross-linked polymer brushes: Optimization with an experimental design approach

Proposing a novel catalyst that achieves catalytic hydrolysis of metal hydrides is an important stage in developing a hydrogen storage system. In this study, a cross-linked gel brush-cobalt (0) composite (Co@P4VP_GB@PMC) has been synthesized to obtain hydrogen from NaBH₄ solution. The morphology, structure, and composition of the obtained catalyst have been characterized by, FTIR, SEM, EDX, BET, XRD, ICP-MS and XPS. The parameters that significantly affect the hydrolysis of NaBH₄ (such as NaBH₄ concentration, NaOH amount, catalyst amount, and temperature) have been investigated using response surface methodology (RSM), an optimization method that has gained increasing importance in recent years. The hydrogen generation rate (HGR) was 4499 mL/min g_cat for Co@P4VP_GB@PMC when the NaBH₄ amount was 241.52 mM, NaOH amount 5 wt%, catalyst amount 10.55 mg and temperature 58.9 °C. Moreover, the apparent activation energy (E_a) for the catalytic hydrolysis reaction has been 41.27 kJmol^-1 obtained under optimum conditions. Additionally, the Co@P4VP_GB@PMC catalyst displayed significant reusability performance for up to five cycles without major loss of its activity. Compared with metal catalysts, this new cross-linked polymer gel brush-cobalt catalyst has excellent potential applications for hydrogen production by hydrolysis of metal hydrides due to its simple synthesis, low cost, and the easy availability of raw materials.     

Carbon-supported Ni1−x@Ptx (x = 0.32, 0.43, 0.60, 0.67, and 0.80) core-shell nanoparticles as catalysts for hydrogen generation from hydrolysis of ammonia borane

We report on the carbon supported Ni core-Pt shell Ni_1−x@Pt_x/C (x = 0.32, 0.43, 0.60, 0.67, and 0.80) nanoparticles as catalysts for hydrogen generation from hydrolysis of ammonia borane (NH₃BH₃). The catalysts are prepared through a polyol synthesis process with oleic acid as the surfactant. The structure, morphology, and chemical composition of the obtained samples are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) equipped with energy dispersive X-ray (EDX), inductively coupled plasma emission spectroscopy (ICP), and nuclear magnetic resonance (NMR). The results show that the Ni core-Pt shell nanoparticles are uniformly dispersed on the carbon surface with the diameters of 2-4 nm, and furthermore, the catalysts show favorable performance toward the hydrolysis of NH₃BH₃. Among the nanoparticles, Ni_0.33@Pt_0.67/C displays the highest catalytic activity, delivering a high hydrogen release rate of 5469 mL min⁻¹ g⁻¹ and a low activation energy of 33.0 kJ mol⁻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.     

Ultrafine palladium nanoparticles anchoring graphene oxide-ionic liquid grafted chitosan self-assembled materials: The novel organic-inorganic hybrid catalysts for hydrogen generation in hydrolysis of ammonia borane

The novel graphene oxide-ionic liquid grafted chitosan composites (denoted as GO-ILCS) are firstly prepared via a self-assembly process. Then, they are used to anchor ultrafine palladium nanoparticles by the in-situ reduction of palladium chloride with sodium borohydride. The resultant Pd(0)/GO-ILCS organic-inorganic hybrid catalysts are characterized by various techniques and used to catalyze the hydrolytic dehydrogenation of ammonia borane (NH₃BH₃, AB) under ambient conditions. The results reveal that the palladium nanoparticles are highly dispersed on GO-ILCS and the Pd(0)/GO-ILCS catalysts exhibit high catalytic activity and excellent reusability in the reaction. The turnover frequency (TOF) is as high as 25.6 $\mathrm{mo}{\mathrm{l}}_{{\mathrm{H}}_{\mathrm{2}}}\mathrm{·mo}{\mathrm{l}}_{\mathrm{Pd}}^{\mathrm{-1}}\mathrm{·mi}{\mathrm{n}}^{\mathrm{-1}}$ and the catalytic activity does not decrease obviously after six runs. The orders of palladium and AB concentrations are 1.00 and 0.33 in the catalytic reaction, respectively. Notably, the activation energy of the reaction (Ea = 38 kJ mol^?1) over the resultant catalysts is obviously lower than most of the palladium-based catalysts reported previously. It is expected the Pd(0)/GO-ILCS catalysts are of exciting potential in the field of hydrogen energy.     

Hydrogen evolution from hydrolysis of ammonia borane catalyzed by Rh/g-C3N4 under mild conditions

Developing effective catalysts for hydrogen evolution from hydrolysis of ammonia borane (AB) is of great significance considering the useful applications of hydrogen. Herein, graphitic carbon nitride (g-C₃N₄) prepared through the simply pyrolysis of urea was employed as a support for Rh nanoparticles (NPs) stabilization. The in-situ generated Rh NPs supported on g-C₃N₄ with an average size of 3.1 nm were investigated as catalysts for hydrogen generation from the hydrolysis of AB under mild conditions. The Rh/g-C₃N₄ catalyst exhibits a high turnover frequency of 969 mol H₂· (min·mol_Rh)^?1 and a low activation energy of 24.2 kJ/mol. The results of the kinetic studies show that the catalytic hydrolysis of AB over the Rh/g-C₃N₄ catalyst is a zero-order reaction with the AB concentration and a first-order reaction with the Rh concentration. This work demonstrates that g-C₃N₄ is a useful support to design and synthesis of effective Rh-based catalyst for hydrogen-based applications.     

Oxygen vacancies and morphology engineered Co3O4 anchored Ru nanoparticles as efficient catalysts for ammonia borane hydrolysis

Developing efficient but facile strategies to modulate the catalytic activity of Ru deposited on metal oxides is of broad interest but remains challenging. Herein, we report the oxygen vacancies and morphological modulation of vacancy-rich Co₃O₄ stabilized Ru nanoparticles (NPs) (Ru/V_O-Co₃O₄) to boost the catalytic activity and durability for hydrogen production from the hydrolysis of ammonia borane (AB). The well-defined and small-sized Ru NPs and V_O-Co₃O₄ induced morphology transformation via in situ driving V_O-Co₃O₄ to 2D nanosheets with abundant oxygen vacancies or Co²⁺ species considerably promote the catalytic activity and durability toward hydrogen evolution from AB hydrolysis. Specifically, the Ru/V_O-Co₃O₄ pre-catalyst exhibits an excellent catalytic activity with a high turnover frequency of 2114 min^?1 at 298 K. Meanwhile, the catalyst also shows a high durability toward AB hydrolysis with six successive cycles. This work establishes a facile but efficient strategy to construct high-performance catalysts for AB hydrolysis.     

Silica embedded cobalt(0) nanoclusters: Efficient, stable and cost effective catalyst for hydrogen generation from the hydrolysis of ammonia borane

Cobalt(0) nanoclusters embedded in silica (Co@SiO₂) were prepared by a facile two-step procedure. In the first step, the hydrogenphosphate anion (HPO₄²⁻) stabilized cobalt(0) nanoclusters were in situ generated from the reduction of cobalt(II) chloride during the hydrolysis of sodium borohydride (NaBH₄) in the presence of stabilizer. Next, HPO₄²⁻ anion-stabilized cobalt(0) nanoclusters were embedded in silica formed by in situ hydrolysis and condensation of tetraethylorthosilicate added as ethanol solution. Co@SiO₂ can be separated from the solution by vacuum filtration and characterized by UV-Vis electronic absorption spectroscopy, TEM, SEM-EDX, ATR-IR and ICP-OES techniques. Co@SiO₂ are found to be highly active and stable catalysts in the hydrolysis of ammonia borane (AB) even at low cobalt concentration and room temperature. They provide an initial turnover frequency of 13.3 min⁻¹ and 24,400 total turnovers over 52 h in the hydrolysis of AB at 25.0 ± 0.5 °C. Moreover, Co@SiO₂ retain 72% and 74% of the initial activity after ten runs recyclability and five cycles reusability test in the hydrolysis of AB, respectively. The kinetics of hydrogen generation from the hydrolysis of AB catalyzed by Co@SiO₂ was studied depending on the catalyst concentration, substrate concentration, and temperature. The activation parameters of this catalytic reaction were also determined from the evaluation of the kinetic data.     

Tungsten(VI) oxide supported rhodium nanoparticles: Highly active catalysts in hydrogen generation from ammonia borane

Herein, we report the use of tungsten(VI) oxide (WO₃) as support for Rh⁰ nanoparticles. The resulting Rh⁰/WO₃ nanoparticles are highly active and stable catalysts in H₂ generation from the hydrolysis of ammonia borane (AB). We present the results of our investigation on the particle size distribution, catalytic activity and stability of Rh⁰/WO₃ catalysts with 0.5%, 1.0%, 2.0% wt. Rh loadings in the hydrolysis reaction. The results reveal that Rh⁰/WO₃ (0.5% wt. Rh) is very promising catalyst providing a turnover frequency of 749 min^?1 in releasing 3.0 equivalent H₂ per mole of AB from the hydrolysis at 25.0 °C. The high catalytic activity of Rh⁰/WO₃ catalyst is attributed to the reducible nature of support. The report covers the results of kinetics study as well as comparative investigation of activity, recyclability, and reusability of colloidal(0) nanoparticles and Rh⁰/WO₃ (0.5 % wt. Rh) catalyst in the hydrolysis reaction.     

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.     

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

Zeolite confined palladium(0) nanoclusters were prepared by a two step procedure: incorporation of Pd²⁺ ions into the zeolite-Y by ion-exchange followed by the reduction of Pd²⁺ ions in the supercages of zeolite-Y with sodium borohydride at room temperature. Zeolite confined palladium(0) nanoclusters are stable enough to be isolated as solid materials and characterized by ICP-OES, XRD, HRTEM, SEM, X-ray photoelectron spectroscopy and N₂ adsorption technique. These nanoclusters are isolable, redispersible and reusable as an active catalyst in the hydrolysis of ammonia-borane solution. Zeolite confined palladium(0) nanoclusters provide 15,600 turnovers in hydrogen generation from the hydrolysis of ammonia-borane at 25.0 ± 0.1 °C.     

Hydrogen release by thermolysis of ammonia borane NH3BH3 and then hydrolysis of its by-product [BNHx]

Ammonia borane (AB) is one of the most attractive hydrides owing to its high hydrogen density (19.5 wt%). Stored hydrogen can be released by thermolysis or catalyzed hydrolysis, both routes having advantages and issues. The present study has envisaged for the first time the combination of thermolysis and hydrolysis, AB being first thermolyzed and then the solid by-product believed to be polyaminoborane [NH₂BH₂]_n (PAB) being hydrolyzed. Herein we report that: (i) the combination is feasible, (ii) PAB hydrolyzes in the presence of a metal catalyst (Ru) at 40 °C, (iii) a total of 3 equiv. H₂ is released from AB and PAB-H₂O, (iv) high hydrogen generation rates can be obtained through hydrolysis, and (v) the by-products stemming from the PAB hydrolysis are ammonium borates. The following reactions may be proposed: AB → PAB + H₂ and PAB + xH₂O → 2H₂ + ammonium borates. All of these aspects as well as the advantages and issues of the combination of AB thermolysis and PAB hydrolysis are discussed.     

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.     

Co3xCu3-3x(PO4)2 microspheres,a novel non-precious metal catalyst with superior catalytic activity in hydrolysis of ammonia borane for hydrogen production

Development of robust and cheap catalyst for fast hydrogen evolution from ammonia borane (AB) aqueous solution is an interesting and important topic in the field of hydrogen energy. Herein, a novel non-precious Co_3xCu_3-3x(PO₄)₂ catalyst possessing high reactivity in AB hydrolysis has been developed for the first time. By tuning the molar ratio of Co and Cu, a series of Co_3xCu_3-3x(PO₄)₂ with different x were synthesized and the catalytic behavior in AB hydrolysis was examined. At the optimal x of 0.8, an ultrahigh turnover frequency of 72.6 min⁻¹ was achieved. Additionally, the synergistic effect between Cu₃(PO₄)₂ and Co₃(PO₄)₂ was experimentally confirmed, and the reaction kinetics of AB hydrolysis catalyzed by Co_2.4Cu_0.6(PO₄)₂ were investigated. This work provides a simple route and some new insights for the fabrication of a cheap P-containing catalyst with robust catalytic performance.