Hexagonal boron nitride supported ruthenium nanoparticles as highly active catalysts for ammonia borane hydrolysis

Ammonia borane (AB) hydrolysis is a comparative strategy for developing the sustainable hydrogen economy. Considering the hydrolysis cannot occur kinetically at low temperature, a suitable catalyst is indispensable. In this work, the dispersed ruthenium nanoparticles are stabilized on hexagonal boron nitride (h-BN) via an adsorption-in situ reduction procedure. Various characterization techniques are adopted for elucidating the structure-performance relationship of the obtained catalysts for the hydrolytic dehydrogenation of AB. In the presence of the resultant Ru/h-BN catalysts, the corresponding turnover frequency (1177.5 min^?1) in alkaline solution at 303 K and the apparent activation energy (24.1 kJ mol^?1) are superior to most literature previously reported. Our work provides a facile fabrication method for metal-based catalysts, which are highly promising in chemical storage material hydrolysis.     

Effective hydrolysis of ammonia borane catalyzed by ruthenium nanoparticles immobilized on graphic carbon nitride

Graphic carbon nitride prepared by the thermal decomposition of urea was used a catalyst support for the in situ immobilization of Ru nanoparticles (NPs) (Ru/g-C₃N₄). The catalytic property of Ru/g-C₃N₄ was investigated in the hydrolysis of ammonia borane (AB) in an aqueous solution under mild conditions. Results show that the in situ generated Ru NPs are well dispersed on the surface of g-C₃N₄ with a mean particle size of 2.8 nm. The catalytic performance for AB hydrolysis indicates that 3.28 wt% Ru/g-C₃N₄ exhibits excellent catalytic activity with a high turnover frequency number of 313.0 mol H₂ (mol Ru·min)⁻¹ at room temperature. This strategy may provide an eco-friendly catalytic system for developing a sustainable catalytic route to hydrogen production.     

Alumina nanofiber-stabilized ruthenium nanoparticles: Highly efficient catalytic materials for hydrogen evolution from ammonia borane hydrolysis

Effective catalysts for hydrogen generation from ammonia borane (AB) hydrolysis should be developed for the versatile applications of hydrogen. In this study, ruthenium nanoparticles (NPs) supported on alumina nanofibers (Ru/Al₂O₃-NFs) were synthesized by reducing the Ru(Ш) ions impregnated on Al₂O₃-NFs during AB hydrolysis. Results showed that the Ru NPs with an average size of 2.9 nm were uniformly dispersed on the Al₂O₃-NFs support. The as-synthesized Ru/Al₂O₃-NFs exhibited a high turnover frequency of 327 mol H₂ (mol Ru min)^?1 and an activation energy of 36.1 kJ mol^?1 for AB hydrolysis at 25 °C. Kinetic studies showed that the AB hydrolysis catalyzed by Ru/Al₂O₃-NFs was a first-order reaction with regard to the Ru concentration and a zero-order reaction with respect to the AB concentration. The present work reveals that Ru/Al₂O₃-NFs show promise as a catalyst in developing a highly efficient hydrogen storage system for fuel cell 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.     

Magnetically recyclable Ni@h-BN composites for efficient hydrolysis of ammonia borane

The magnetic Ni@h-BN composites containing the uniform Ni nanoparticles supported on h-BN nanosheets have been prepared via a facile solvothermal method. The as-prepared samples show high catalytic performance for H₂ generation from the ammonia borane aqueous solution, especially for the Ni@h-BN with 25.0 wt% Ni content. Moreover, the Ni@h-BN composites possess a good ferromagnetic property at room temperature, endowing them with rapid magnetic separation to recycle. The kinetics of the hydrolysis of ammonia borane over the Ni@h-BN composites were further investigated in detail. It is found that the hydrogen generation was highly dependent on the catalyst amount and the reaction temperature. The activation energy of the hydrolysis reaction of ammonia borane is found to be 47.3 kJ mol^?1 over the Ni@h-BN with 25.0 wt% Ni content. Considering the good catalytic activities for H₂ release, the Ni@h-BN composites are expected to find important application in fuel cells and the related fields.     

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.     

Ruthenium nanoparticles immobilized in montmorillonite used as catalyst for methanolysis of ammonia borane

Ammonia borane (AB) is an intriguing molecular crystal material with extremely high hydrogen density. In the present study, we prepared ruthenium (Ru) nanoparticles immobilized in montmorillonite (MMT) and examine its catalytic effect on the methanolysis reaction of AB. The Ru/MMT catalyst was prepared by cation-exchange method followed by hydrogen reduction at elevated temperatures. Property examinations found that the Ru/MMT catalyst was highly effective and robust for promoting the methanolysis reaction of AB. For example, the methanolysis system employing Ru/MMT catalyst exhibited an average hydrogen generation rate of 29 L min⁻¹ g⁻¹ (Ru). The catalyst at its twentieth usage retained 95% of its initial activity and ensured 100% conversion of AB. Kinetics studies found that the methanolysis reaction of AB employing Ru/MMT catalyst follows first-order kinetics with respect to AB concentration and catalyst amount, respectively.     

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

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

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.     

Catalytically active rhodium nanoparticles stabilized by nitrogen doped carbon for the hydrolysis of ammonia borane

We report the preparation of an ammonia borane hydrolysis catalyst for use in hydrogen production by dispersing Rh nanoparticles on a nitrogen-doped carbon (NPC) support. The resulting Rh/NPC catalyst had a measured turnover frequency of 473.5 min^?1, higher than that of many previously reported Rh-based catalysts. This catalyst could also be reused eight times. The large surface area and abundant nitrogen-functional species of NPCs facilitate dispersion of Rh nanoparticles on their surface, providing numerous catalytically active sites for ammonia borane hydrolysis, thereby leading to high catalytic activity. This study demonstrates that NPC support can be used to prepare highly active catalysts.     

Catalytic hydrolysis of ammonia borane via magnetically recyclable copper iron nanoparticles for chemical hydrogen storage

In this work, a series of new Cu_1−xFe_x alloy nanoparticles (NPs) have been successfully in situ synthesized by a very simple method and used as catalysts for hydrogen generation from the aqueous solution of ammonia borane (AB) under ambient atmosphere at room temperature. The prepared nanoalloys exhibit excellent catalytic activity, especially for Cu_0.33Fe_0.67 sample outperform the activity of monometallic counterparts, and even of Cu@Fe core–shell NPs. By using an external magnet, these catalysts can be readily separated from the solution for recycle purpose, and can keep the high activity even after 8 times of recycle under ambient atmosphere. The hydrolysis activation energy for the Cu_0.33Fe_0.67 alloy NPs was measured to be approximately 43.2 kJ/mol, which is lower than most of the reported activation energy values for the same reaction using many different catalysts except for some noble-metal containing catalysts, indicating the superior catalytic performance of Cu_0.33Fe_0.67 nanocatalysts.     

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.     

Efficient hydrogen production from ammonia borane hydrolysis catalyzed by TiO2-supported RuCo catalysts

Hydrolysis of ammonia borane provides a reliable pathway for hydrogen production, while suitable catalysts are indispensable to make the hydrolysis reaction reach a considerable rate. In the present work, a series of TiO₂-supported RuCo catalysts have been fabricated by coprecipitation and subsequent reduction of Ru³⁺ and Co²⁺ on the surface of TiO₂ nanoparticles. Transmission electron microscopy and elemental mapping have verified the good distribution of metal species in the catalysts. The fabricated catalysts have shown excellent performance for catalyzing ammonia borane hydrolysis, especially in alkaline solutions with 0.5 M NaOH. For Ru₁Co₉/TiO₂ in which Ru/Co molar ratio is 1:9, the active energy of catalyzed ammonia borane hydrolysis is 33.25 kJ/mol, and a turnover frequency based on Ru as high as 1408 mol_H2/(mol_Ru·min) is obtained at 25 °C. Moreover, when different types of TiO₂ substrates are used, anatase TiO₂-supported catalysts show better catalytic activity than their counterparts with rutile TiO₂ as substrate or mixture of anatase and rutile TiO₂ as substrate.     

Enhanced catalytic performance of CuNi bimetallic nanoparticles for hydrogen evolution from ammonia borane hydrolysis

Ammonia borane (AB, NH₃BH₃) hydrolysis is an effective way to safely generate hydrogen. However, a suitable catalyst is indispensable because the hydrolytic reaction cannot take place kinetically at room temperature. In this work, CuNi alloy nanoparticles are immobilized on porous graphitic carbon nitride (g-C₃N₄) with a facile adsorption-chemical reduction method. Benefiting from the hierarchical porous structure of the support, the interesting alloy effect of Cu and Ni, as well as the synergistic effect between g-C₃N₄ and the CuNi alloys, the optimal Cu_0·7Ni_0.3/g-C₃N₄ catalyst displays excellent catalytic performance in AB hydrolysis, such as high turnover frequency (2.08 min⁻¹, at 303 K), low apparent activation energy (23.58 kJ mol⁻¹), and satisfactory durability. The results verify that the optimal catalyst has particular potential in hydrogen energy utilization due to the advantages such as the facile preparation procedure, low cost and excellent catalytic behavior.     

Ruthenium(0) nanoparticles supported on silica coated Fe3O4 as magnetically separable catalysts for hydrolytic dehydrogenation of ammonia borane

Ruthenium(0) nanoparticles supported on bare or silica-coated magnetite are prepared by impregnation of ruthenium(III) ions followed by their reduction with aqueous solution of sodium borohydride on the surface of support. These magnetically isolable catalysts are used in hydrogen generation from the hydrolysis of ammonia borane at room temperature. They conserve their initial catalytic activity even after the fifth reuse in the hydrolysis reaction. Ruthenium(0) nanoparticles supported on bare magnetite and silica-coated magnetite provide turnover frequency values of 29 min^?1 and 127 min^?1 and in hydrolytic dehydrogenation of ammonia borane at 25.0 ± 0.1 °C. Thus, coating of the surface of magnetite with silica results in a significant enhancement in catalytic activity of ruthenium(0) nanoparticles in hydrogen generation from the hydrolysis of ammonia borane.     

Ru nanoparticles loaded on tannin immobilized collagen fibers for catalytic hydrolysis of ammonia borane

A kind of Ru-based catalyst was prepared by using a natural polyphenolic polymer (bayberry tannin, BT) immobilized on collagen fiber (CF) as the stabilizer and carrier of Ru nanoparticles (NPs) and characterized to detect its main physicochemical properties. The CF-BT-Ru catalyst was found to be in an orderly fiber morphology with Ru NPs with about diameter of 2.6 nm highly distributed on the surface. The research on catalytic activity of CF-BT-Ru focused on the hydrolysis of ammonia borane (AB) to produce hydrogen. The influences of Ru loading, Ru dosage, AB concentration and temperature on the catalytic AB hydrolysis were investigated in detail, and the related thermodynamic parameters (activation energy (E_a), activation entropy (△S), activation enthalpy (△H) and Gibbs free energy (△G)) were calculated. The experimental results indicated that CF-BT-Ru exhibited high catalytic activity. Its turnover frequency (TOF) was as high as 322 ${\text{mol}}_{{\text{H}}_2}?{\text{mol}}_{\text{Ru}}^{?1}?{\text{min}}^{?1}$ and E_a was as low as 32.41 kJ mol^?1 for AB hydrolysis. Moreover, CF-BT-Ru exhibited satisfied reusability and stability. Its activity lost only one-fifth and no obvious agglomeration and leakage of Ru NPs were found after repeated use for 5 times.     

One-pot co-reduction synthesis of orange-like Pd@Co@P nanoparticles supported on rGO for catalytic hydrolysis of ammonia borane

Transition metal phosphide based orange-like Pd@Co@P nanoparticles supported on reduced graphene oxide (Pd@Co@P/rGO) have been synthesized by a one-pot co-reduction at room temperature using methylamine borane (MeAB) as the reducing agent. The prepared Pd@Co@P/rGO nanoparticles were characterized by powder X-ray diffraction (XRD), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), selected area electron diffraction (SAED) and confocal Raman microscopy (Raman). Compared with Pd/rGO and Pd@Co/rGO, the Pd@Co@P/rGO catalyst has higher catalytic activity for the hydrolytic production of ammonia borane (AB) with the turnover frequency value (TOF) of 127.57 min⁻¹ and the activation energy of 39.05 kJ mol⁻¹. This excellent catalytic performance may be caused by the orange-like structure and good dispersion of Pd@Co@P/rGO nanoparticles, and the synergistic electron interactions between palladium, cobalt, and phosphorus.     

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.     

A study of catalytic hydrolysis of concentrated ammonia borane solutions

Ruthenium catalyzed ammonia borane (AB) hydrolysis using aqueous solutions in the range of 5–25 wt% were experimentally studied. The experimental apparatus also included a means for gaseous ammonia sequestration. In addition, the effects of aging on reaction rates and total H₂ conversion were investigated using AB solutions that were stored in a limited-air environment for a maximum of 67 days. The present work provides data on total H₂ conversion, chemical kinetics, solution density, pH value, byproduct solubility, ammonia generation, and long-term storage stability of concentrated aqueous AB solutions.     

Metal-catalyzed hydrolysis of ammonia borane: Mechanism,catalysts, and challenges

Ammonia borane is a promising material for hydrogen storage. In particular, its metal-catalyzed hydrolysis, which can occur under mild conditions and release a high amount (7%–8%) of hydrogen, has attracted considerable recent attention. Most previous studies have sought to improve the hydrolysis rate, leading to a relatively asymmetric research trend, where some potential problems must be overcome before its industrialization. A comprehensive analysis and systematic overview of current research would therefore be helpful to future works. This review first discusses the hydrolysis of ammonia borane in detail. It then summarizes and analyzes recent development of metal catalysts. Some challenges related to the hydrolysis system are also discussed, and finally, some perspectives on emerging issues regarding the future development of this system are provided.