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.     

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.     

RuCo bimetallic alloy nanoparticles immobilized on multi-porous MIL-53(Al) as a highly efficient catalyst for the hydrolytic reaction of ammonia borane

Well-dispersed bimetallic RuCo alloy nanoparticles (NPs) were successfully immobilized on the multi-porous, water-tolerant metal organic frameworks MIL-53(Al) by a facile solvent impregnation method. Among the RuCo@MIL-53(Al) with different Ru/Co molar ratios, the Ru₁Co₁@MIL-53(Al) performed better and was superior to Ru@MIL-53(Al) and single RuCo NPs for the hydrolysis of ammonia borane (AB, NH₃BH₃), owing to the synergistic effect caused by the electronic and geometric interactions between Ru and Co atoms and bi-functional effect generated between the RuCo NPs and the MIL-53(Al) support. Compared with bimetallic Ru₁Ni₁ and Ru₁Cu₁ counterparts loadings, the Ru₁Co₁@MIL-53(Al) also showed better catalytic activity for the hydrolysis of AB. Moreover, the Ru₁Co₁@ MIL-53(Al) presented good durability and reusability in the catalytic reaction, and the activation energy (Ea) and turnover frequency values (TOF) were 34.32 kJ mol^?1 and 87.24 mol H₂ min^?1 (mol Ru)^?1, respectively.     

Enhanced catalytic activity of NiM (M = Cr,Mo, W) nanoparticles for hydrogen evolution from ammonia borane and hydrazine borane

In this work, a series of Ni_1-xM_x (M = Cr, Mo, W) nanoparticles (NPs) have been successfully synthesized via a simple surfactant-aided co-reduction method and employed as highly efficient and cost effective catalysts for hydrogen generation from aqueous solution of ammonia borane (NH₃BH₃, AB) at room temperature. It is found that the as-synthesized NiM NPs (M = Cr, Mo, W) exhibit much higher catalytic performance for the hydrolysis of AB as compared to that of pure Ni NPs. In addition, among all the Ni_1-xM_x (M = Cr, Mo, W) NPs, the Ni_0.9Cr_0.1, Ni_0.9Mo_0.1, and Ni_0.8W_0.2 NPs show the highest catalytic activities with the turnover frequency (TOF) values of 10.7, 27.3 and 25.0 mol H₂ (mol metal min)^?1, respectively. Remarkably, these optimized NiM catalysts can also perform efficiently in the hydrolysis of hydrazine borane (N₂H₄BH₃, HB). The present low-cost and high-performance of the NiM catalysts system may encourage the practical application of AB and HB as the promising chemical hydrogen storage materials.     

Carbon-supported small Rh nanoparticles prepared with sodium citrate: Toward high catalytic activity for hydrogen evolution from ammonia borane hydrolysis

Hydrogen generation from the hydrolysis of ammonia borane (AB) over heterogeneous catalysts is essential for practical applications. Herein, efficient hydrogen evolution from AB hydrolysis over the carbon-supported Rh nanoparticles synthesized with sodium citrate (Rh/C-SC) was achieved at 25 °C. The turnover frequency value of Rh/C-SC was 336 mol H₂ (mol_Rh min)^?1, whereas that of Rh/C catalyst only yielded a value of 134 mol H₂ (mol_Rh min)^?1. The improvement of the catalytic performance of Rh/C-SC catalyst could be attributed to the small Rh particles with highly active surface areas, which were prepared by using sodium citrate as the stabilizing agent. This result indicates that sodium citrate can be applied as a useful stabilizing agent for synthesizing active metal nanoparticles, thus highly promoting the practical application of AB system for fuel cells.     

Mo remarkably enhances catalytic activity of Cu@MoCo core-shell nanoparticles for hydrolytic dehydrogenation of ammonia borane

Ammonia borane (AB) has been identified as one of the most promising candidates for chemical hydrogen storage. However, the practical application of AB for hydrogen production is hindered by the need of efficient and inexpensive catalysts. For the first time, we report that the incorporation of Mo into Cu@Co core-shell structure can significantly improve the catalytic efficiency of hydrogen generation from the hydrolysis of AB. The Cu_0.81@Mo_0.09Co_0.10 core-shell catalyst displays high catalytic activity towards the hydrolysis dehydrogenation of AB with a turnover frequency (TOF) value of 49.6 molH₂ mol_cat^?1 min^?1, which is higher than most of Cu-based catalysts ever reported, and even comparable to those of noble-metal based catalysts. The excellent catalytic performance is attributed to the multi-elements co-deposition effect and electrons transfer effect of Cu, Mo and Co in the tri-metallic core-shell NPs.     

Salicylaldimine-Ni complex supported on Al2O3: Highly efficient catalyst for hydrogen production from hydrolysis of sodium borohydride

In this study, the Ni-based complex catalyst containing nickel of 1% supported on Al₂O₃ is used as for the hydrogen production from NaBH₄ hydrolysis. The maximum hydrogen production rate from hydrolysis of NaBH₄ with Ni-based complex catalyst supported on Al₂O₃ containing nickel of 1% is 62535 ml min^?1 g^?1 (complex catalyst containing 1 wt% Ni). The resulting complex catalyst is characterised by XRD, XPS, SEM, FT-IR, UV, and BET surface area analyses. The Arrhenius activation energy is found to be 27.29 kJ mol^?1 for the nickel-based complex catalyst supported on Al₂O₃. The reusability of the catalyst used in this study has also been investigated. The Ni-based complex catalyst supported on Al₂O₃ containing nickel of 1% is maintained the activity of 100% after the fifth use, compared to the first catalytic use. The n value for the reaction rate order of NaBH₄ is found to be about 0.33.     

Kinetic performance of hydrogen generation enhanced by AlCl3 via hydrolysis of MgH2 prepared by hydriding combustion synthesis

Magnesium hydride (MgH₂) is a very promising hydrogen storage material and it has been paid more and more attention on the application of supplying hydrogen on-board because the theoretical hydrogen yield is up to 1703 mL/g when it reacts with water. However, the hydrolysis reaction is inhibited rapidly by the passivation layer of Mg(OH)₂ formed on the surface of MgH₂. This paper reports that high purity MgH₂ (～98.7 wt%) can be readily obtained by the process of hydriding combustion synthesis (HCS) and the hydrogen generation via hydrolysis of the as-prepared HCSed MgH₂ can be dramatically enhanced by the addition of AlCl₃ in hydrolysis solutions. An excellent kinetics of hydrogen generation of 1487 mL/g in 10 min and 1683 mL/g in 17 min at 303 K was achieved for the MgH₂-0.5 M AlCl₃ system, in which the theoretical hydrogen yield (1685 mL/g) of the HCSed product was nearly reached. The mechanism of the hydrolysis kinetics enhancement was demonstrated by the generation of a large amounts of H⁺ from the Al³⁺ hydrolysis and the pitting corrosion (Cl^?) of the Mg(OH)₂ layer wrapped on the surface of MgH₂ even at a low temperature. In addition, the apparent activation energies for the MgH₂ hydrolysis in the 0.1 M AlCl₃ and 0.5 M AlCl₃ solutions are decreased to 34.68 kJ/mol and 21.64 kJ/mol, respectively, being far superior to that of reported in deionized water (58.06 kJ/mol). The results suggest that MgH₂ + AlCl₃ system may be used as a promising hydrogen generation system in practical application of supplying hydrogen on-board.     

Poly(N-vinyl-2-pyrrolidone)-stabilized ruthenium supported on bamboo leaf-derived porous carbon for NH3BH3 hydrolysis

In this work, poly(N-vinyl-2-pyrrolidone) (PVP)-stabilized ruthenium nanoparticles (NPs) supported on bamboo leaf-derived porous carbon (Ru/BC) has been synthesized via a one-step procedure. The structure and morphology of the as-synthesized samples were characterized by means of X-ray diffraction (XRD), X-ray photoelectron spectrometry (XPS), scanning electron microscope (SEM) and transmission electron microscope (TEM). As a catalyst for hydrogen generation from the hydrolysis of ammonia-borane (AB, NH₃BH₃) at room temperature, Ru/BC stabilized with 1 mg of PVP exhibited high activity (TOF = 718 mol_H2·mol_Ru⁻¹·min⁻¹) and low activation energy (E_a = 22.8 kJ mol⁻¹). In addition, the catalyst could be easily recovered and showed fairly good recyclability with 55.6% of the initial catalytic activity retained after ten experimental cycles, which confirmed that PVP could stabilize the Ru NPs and prevent their agglomeration on BC surface. Our results suggest that PVP-stabilized Ru/BC is a highly efficient catalyst for the hydrolysis of AB.     

Nanosizing ammonia borane with nickel – An all-solid and all-in-one approach for H2 generation by hydrolysis

Ammonia borane NH₃BH₃ (AB) and nickel (Ni) have been considered together as an all-solid and all-in-one material for H₂ generation by hydrolysis at 20–50 °C. Our novel approach, denoted Ni/AB, consists of AB nanoparticles within a Ni matrix. Upon contact with water, Ni/AB readily hydrolyzes and liberates H₂ with a turnover frequency of 13.8 mol(H₂) mol_Ni^?1 min^?1 at 43.3 °C. The apparent activation energy, determined over the temperature range 23.5–50.4 °C, is low, with 19.5 ± 4.1 kJ mol^?1. These results imply that such a Ni matrix embedding AB acts as an effective catalyst. Beyond the catalytic performance, this is the first report of the successful utilization of an all-solid and all-in-one approach for the hydrolysis of AB, and the work brings unique perspectives for one-shot catalytic systems.     

Noble-metal-free Co@Co2P/N-doped carbon nanotube polyhedron as an efficient catalyst for hydrogen generation from ammonia borane

Developing an efficient catalyst for hydrogen (H₂) generation from hydrolysis of ammonia borane (AB) to significantly improve the activity for the hydrogen generation from AB is important for its practical application. Herein, we report a novel hybrid nanostructure composed of uniformly dispersed Co@Co₂P core-shell nanoparticles (NPs) embedded in N-doped carbon nanotube polyhedron (Co@Co₂P/N–CNP) through a carbonization-phosphidation strategy derived from ZIF-67. Benefiting from the electronic effect of P doping, high dispersibility and strong interfacial interaction between Co@Co₂P and N-CNTs, the Co@Co₂P/N–CNP catalyst exhibits excellent catalytic performance towards the hydrolysis of AB for hydrogen generation, affording a high TOF value of 18.4 mol H₂ mol metal^?1 min^?1 at the first cycle. This work provides a promising lead for the design of efficient heterogeneous catalysts towards convenient H₂ generation from hydrogen-rich substrates in the close future.     

Hydrolytic dehydrogenation of ammonia borane and methylamine borane catalyzed by graphene supported Ru@Ni core–shell nanoparticles

Ru@Ni core–shell nanoparticles (NPs) supported on graphene have been synthesized by one-step in situ co-reduction of aqueous solution of ruthenium (III) chloride, nickel (II) chloride, and graphene oxide (GO) with ammonia borane (AB) as the reducing agent under ambient condition. The as-synthesized NPs exhibit much higher catalytic activity for hydrolytic dehydrogenation of AB than the monometallic, bimetallic alloy (RuNi/graphene), and graphene-free core–shell (Ru@Ni) counterparts. Additionally, the Ru@Ni/graphene NPs facilitate the hydrolysis of AB, with the turnover frequency (TOF) value of 340 mol H₂ min⁻¹ (mol Ru)⁻¹, which is among the highest value reported on Ru-based NPs so far, and even higher than the reversed Ni@Ru NPs. Furthermore, the as-prepared NPs exert satisfied durable stability and magnetically recyclability for the hydrolytic dehydrogenation of AB and methylamine borane (MeAB). Moreover, this simple synthetic method can be extended to other Ru-based bimetallic core–shell systems for more applications.     

Recoverable Ni2Al3 nanoparticles and their catalytic effects on Mg-based nanocomposite during hydrogen absorption and desorption cycling

The Mg-3.9 wt% Ni₂Al₃ nanocomposite is produced by hydrogen plasma-metal reaction method. The particle size of Mg is in range of 40–160 nm with an average size of 90 nm. The Ni₂Al₃ nanoparticles (NPs) of about 9 nm uniformly disperse on the surface of Mg NPs and in situ transform to Mg₂NiH_0.3 and Al after hydrogen absorption process. Surprisingly, the Mg₂NiH_0.3 and Al can recover to the initial state of Ni₂Al₃ after hydrogenation/dehydrogenation cycle. The Mg-Ni₂Al₃ nanocomposite shows enhanced hydrogen sorption rate and storage capacity. It can quickly uptake 6.4 wt% H₂ within only 10 min at 573 K, and release 6.1 wt% H₂ within 10 min at 623 K. The apparent activation energies for hydrogenation and dehydrogenation are calculated to be 55.4 and 115.7 kJ mol^?1 H₂. The enhanced hydrogen storage performances of the Mg-Ni₂Al₃ nanocomposite are attributed to both the nanostructure of Mg and the catalytic effects of Ni₂Al₃ NPs.     

The Hydroloysis of ammonia borane by using Amberlyst-15 supported catalysts for hydrogen generation

Resin catalysts have the advantage of having various properties and long lifetime due to their ability to be regenerated easily, which makes them attractive supports. In this paper, a comparative study was conducted to optimize the dehydrogenation reaction condition using two different types of support materials: alumina (Al₂O₃), and Amberlyst-15 and to improve the catalytic activity as well as preparing an efficient and low-cost system for practical application, ruthenium metal catalyst was incorporated on Amberlyst-15 resin (a sulfonic acid type based upon a styrene-divinylbenzene copolymer) to release H₂ via hydrolytic dehydrogenation of ammonia borane. Using ruthenium (Ru) catalysts based on Amberlyst-15 support material and comparing the results with Al₂O₃ as the common supporting material is considered to be studied for the first time. The effect of temperature (20–50 °C), the initial ammonia borane concentration (0.05–0.5 %wt), and catalyst amount (0.2–0.5 g) on the produced H₂ yield was also investigated. Ru@Amberlyst-15 nanoparticle was discovered to be an effective catalyst for hydrogen evolution via the hydrolysis of ammonia borane with a turnover frequency value (TOF) of 343.3 min^?1, while Ru@Al₂O₃ yielded a TOF of 87.5 min^?1 at the room temperature. Therefore, it can be concluded that the Amberlyst-15 supporting effect on ruthenium metal leads an increase in the hydrogen production rate.     

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.     

Catalytic effects of V and V2O5 on hydrogen storage property of Mg17Al12 alloy

A Mg₁₇Al₁₂ alloy was synthesized via sintering, and the catalytic effects of V and V₂O₅ on the hydrogen (H₂)-storage properties of this alloy were investigated. The results revealed that the hydrogenation/dehydrogenation temperature of Mg₁₇Al₁₂ decreased markedly and the reversible hydrogen storage properties improved with the addition of V or V₂O₅. For example, at 250 °C, the Mg₁₇Al₁₂ alloy underwent hydrogenation only and a hydrogen absorption capacity of 2.22 wt.% was realized. However, with the addition of V and V₂O₅, (i) reversible hydrogen absorption/desorption occurred, (ii) the hydrogen absorption capacity increased to 2.95 wt.% and 3.35 wt.%, and (iii) the hydrogenation/dehydrogenation enthalpy of the Mg₁₇Al₁₂alloy decreased from 65.7/83.1 kJ·mol^?1 to 62.6/69.3 kJ·mol^?1 and 59.9/68.1 kJ·mol^?1, respectively.     

La2O3-modified highly dispersed AuPd alloy nanoparticles and their superior catalysis on the dehydrogenation of formic acid

Formic acid (FA, HCOOH), a convenient and safe hydrogen storage material, has the great potential for fuel cell applications. However, hydrogen generation of FA is inefficient in the presence of heterogeneous catalysts at relatively low temperatures, which remains a big challenge. Herein, La₂O₃-modified highly dispersed AuPd alloy nanoparticles (AuPdLa₂O₃) with small particle size have been successfully anchored on carbon nanotubes (CNTs) by a facile co-reduction route. Moreover, the catalyst exhibits excellent catalytic activity and 100% hydrogen selectivity for hydrogen generation in the formic acid/sodium formate (FA/SF) system with the initial turnover frequency (TOF) value of 589 mol H₂ mol^?1 catalyst h^?1 at 50 °C and 280 mol H₂ mol^?1 catalyst h^?1 even at room temperature (25 °C). The present Au_0.3Pd_0.7-(La₂O₃)_0.6/CNTs with superior catalysis on FA dehydrogenation without any CO generation at room temperature can not only pave the way for practical application of hydrogen storage system, but also can be extended to other catalysis system.     

Facile construction of composition-tuned ruthenium-nickel nanoparticles on g-C3N4 for enhanced hydrolysis of ammonia borane without base additives

Developing high-efficiency and low-cost catalysts for hydrogen evolution from hydrolysis of ammonia borane (AB) is significant and critical for the exploitation and utilization of hydrogen energy. Herein, the in-situ fabrication of well-dispersed and small bimetallic RuNi alloy nanoparticles (NPs) with tuned compositions and concomitant hydrolysis of AB are successfully achieved by using graphitic carbon nitride (g-C₃N₄) as a NP support without additional stabilizing ligands. The optimized Ru₁Ni_7.5/g-C₃N₄ catalyst exhibits an excellent catalytic activity with a high turnover frequency of 901 min^?1 and an activation energy of 28.46 kJ mol^?1 without any base additives, overtaking the activities of many previously reported catalysts for AB hydrolysis. The kinetic studies indicate that the AB hydrolysis over Ru₁Ni_7.5/g-C₃N₄ is first-order and zero-order reactions with respect to the catalyst and AB concentrations, respectively. Ru₁Ni_7.5/g-C₃N₄ has a good recyclability with 46% of the initial catalytic activity retained even after five runs. The high performance of Ru₁Ni_7.5/g-C₃N₄ should be assigned to the small-sized alloy NPs with abundant accessible active sites and the synergistic effect between the composition-tuned Ru–Ni bimetals. This work highlights a potentially powerful and simple strategy for preparing highly active bimetallic alloy catalysts for AB hydrolysis to generate hydrogen.     

Thermocatalytic decomposition of methane over mesoporous Ni/xMgO·Al2O3 nanocatalysts

This paper describes a facile method to produce mesoporous nanostructure Ni/Al₂O₃, Ni/MgO, and Ni/xMgO.Al₂O₃ (x: MgO/Al₂O₃ molar ratio) catalysts prepared by “one-pot” evaporation-induced self-assembly (EISA) method with some modifications for investigating in the thermocatalytic decomposition of methane. Detailed characterizations of the material were performed with X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and N₂ adsorption/desorption, hydrogen temperature-programmed reduction (H₂-TPR), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and temperature-programmed oxidation (TPO). The characterizations demonstrated that the synthesized catalysts with various MgO/Al₂O₃ molar ratios possessed mesoporous structure with the high BET area in the range of 216.79 to 31.74 m² g^?1. The effect of different surfactants and calcination temperatures on the characterizations and catalytic activity of the catalysts were also examined in details. The experimental results showed that the catalysts exhibited high catalytic potential in this process and the 55 wt.% Ni/2 MgO·Al₂O₃ catalyst calcined at 600^οC possessed an acceptable methane conversion (～60%) under the harsh reaction conditions (GHSV = 48000 (mL h^?1 g_cat^?1)).     

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.