CuO–Ru0.3@Co3O4 nanocomposites act as a tandem catalyst for dehydrogenation of ammonia borane and hydrogenation of nitrobenezene

The development of catalysts with high activity for tandem reaction are all the ways pursued by chemists. Herein, CuO–Ru_0.3@Co₃O₄ has been synthesized and used as efficient tandem catalyst to promote the release of hydrogen from hydrolytic dehydrogenation of ammonia borane (AB) to catalyze the hydrogenation of nitrobenezenes (NBs). The catalyst exhibits the TOF of 29.87 min^?1 and provides the apparent activation energy of 45.2 kJ mol^?1 for the hydrolytic dehydrogenation of AB. Additionally, benefited from the magnetic separation capability, up to 99% of its initial catalytic activity is retained after four catalytic cycles.     

Monodisperse PtCu alloy nanoparticles as highly efficient catalysts for the hydrolytic dehydrogenation of ammonia borane

Pt-M alloy nanoparticles (NPs) with well-defined size and compositions exhibit dramatically catalytic performance in chemical reactions. In this work, monodisperse PtCu NPs with controlled size and compositions were synthesized by the co-reduction method in the presence of oleylamine. These NPs have excellent catalytic activities in the hydrolytic dehydrogenation of ammonia borane (AB) and their activities were composition dependent. Among the different-composition PtCu NPs, the Cu₅₀Pt₅₀ NPs exhibit the highest catalytic activity with an initial turnover frequency of 102.5 mol_(hydrogen)·mol_(catalyst)^?1·min^?1 and an apparent activation energy of 36 kJ·mol^?1, which demonstrate the validity of partly replacing Pt by a first-row transition metal on constructing high performance heterogeneous nanocatalysts for the hydrolytic dehydrogenation of AB.     

The doped Co on Rh/Ni@Ni–N–C that weakened the catalytic performance for ammonia borane hydrolysis

Alloy catalyst has been widely studied and used for hydrolytic dehydrogenation of ammonia borane (NH₃BH₃, AB) with excellent catalytic performance due to the synergistic effect of bimetal. Herein, a series of Rh_1-xCo_x/Ni@Ni–N–C catalysts were prepared by an impregnation reduction method. The optimized Rh_0.75Co_0.25/Ni@Ni–N–C catalyst exhibited good catalytic performance with turnover frequency of 223.08 mol_H2 mol_cat^?1 min^?1 at 303 K, but decreased the catalytic performance compared with Rh/Ni@Ni–N–C. According to the XPS and Raman analysis, the RhCo alloy nanoparticles could be loaded at the defect position of Ni@Ni–N–C, and the Co nanoparticles occupied the intercalation between Rh and the defective site of the carrier, which could weaken the catalytic activity of AB hydrolysis. Based on the above research, we proposed the catalytic mechanism of the activation of the RhCo–H species. This work provides a new strategy for designing alloy-supported nano-catalysts.     

Modulating Fischer-Tropsch synthesis performance on the Co3O4@SixAly catalysts by tuning metal-support interaction and acidity

ZIF-67 derived catalysts for Fischer-Tropsch synthesis have attracted much attention in recent years, while there is still a potential to improve their activity and selectivity. In this work, we prepared Si/Al co-immobilized Co₃O₄@Si_xAl_y catalysts by in-situ doping tetraethylorthosilicate and aluminum nitrate during the synthesis of ZIF-67. The effects of different Si/Al ratios on the metal-support interaction, acidity and FTS performance were explored. Results indicated that the Co₃O₄@Si₀Al₄ catalyst exhibited the best FTS performance with the CO conversion as high as 79.9% and CTY (cobalt time yield) value of 19.5 × 10^?5 mol_CO·g_Co^?1·s^?1, which was ascribed to the moderate metal-support interaction and the most active Co sites. Meanwhile, the Co₃O₄@Si₃Al₁ and Co₃O₄@Si₂Al₂ catalysts exhibited higher iso-paraffin and olefin selectivity due to more acidic sites.     

Monodisperse nickel–palladium alloy nanoparticles supported on reduced graphene oxide as highly efficient catalysts for the hydrolytic dehydrogenation of ammonia borane

Addressed herein is the catalysis of reduced graphene oxide-supported monodisperse NiPd alloy nanoparticles (NPs) (rGO-NiPd) in the hydrolytic dehydrogenation of ammonia borane (AB). This is the first example of the use of NiPd alloy NPs as catalyst in the hydrolytic dehydrogenation of AB. Monodisperse NiPd alloy NPs (3.5 nm) were synthesized by co-reduction of nickel(II) acetate and palladium(II) acetylacetonate in oleylamine (OAm) and borane-tert-butylamine complex (BTB) at 100 °C. The current recipe allowed to control the composition of NiPd alloy NPs and to study the composition-controlled catalysis of rGO-NiPd in the hydrolytic dehydrogenation of AB. Among the all compositions tested, the Ni₃₀Pd₇₀ was the most active one with the turnover frequency of 28.7 min⁻¹. The rGO-Ni₃₀Pd₇₀ were also durable catalysts in the hydrolytic dehydrogenation of AB providing 3650 total turnovers in 35 h and reused at six times without deactivation. The detailed reaction kinetics of hydrolytic dehydrogenation of AB revealed that the reaction proceeds first order with respect to the NiPd concentration and zeroth order with respect to the AB concentration. The apparent activation energy of the catalytic dehydrogenation of AB was also calculated to be E_a^app = 45 ± 2 kJ*mol⁻¹.     

Structure-dependent activity and stability of Al2O3 supported Rh catalysts for the steam reforming of n-dodecane

Steam reforming of liquid hydrocarbon fuels is an appealing way for the production of hydrogen. In this work, the Rh/Al₂O₃ catalysts with nanorod (NR), nanofiber (NF) and sponge-shaped (SP) alumina supports were successfully designed for the steam reforming of n-dodecane as a surrogate compound for diesel/jet fuels. The catalysts before and after reaction were well characterized by using ICP, XRD, N₂ adsorption, TEM, HAADF-STEM, H₂-TPR, CO chemisorption, NH₃-TPD, CO₂-TPD, XPS, Al²⁷ NMR and TG. The results confirmed that the dispersion and surface structure of Rh species is quite dependent on the enclosed various morphologies. Rh/Al₂O₃-NR possesses highly dispersed, uniform and accessible Rh particles with the highest percentage of surface electron deficient Rh⁰ active species, which due to the unique properties of Al₂O₃ nanorod including high crystallinity, relatively large alumina particle size, thermal stability, and large pore volume and size. As a consequent, Rh/Al₂O₃-NR catalyst exhibited superior catalytic activity towards steam reforming reactions and hydrogen production rate over other two catalysts. Especially, Rh/Al₂O₃-NR catalyst showed the highest hydrogen production rate of 87,600 mmol g_fuel^?1 g_Rh^?1min^?1 among any Rh-based catalysts and other noble metal-based catalysts to date. After long-term reaction, a significant deactivation occurred on Rh/Al₂O₃–NF and Rh/Al₂O₃-SP catalysts, due to aggregation and sintering of Rh metal particles, coke deposition and poor hydrothermal stability of nanofibrous structure. In contrast, the Rh/Al₂O₃-NR catalyst shows excellent reforming stability with negligible coke formation. No significantly sintering and aggregation of the Rh particles is observed after long-term reaction. Such great catalyst stability can be explained by the role of hydrothermal stable nanorod alumina support, which not only provides a unique environment for the stabilization of uniform and small-size Rh particles but also affords strong surface basic sites.     

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.     

Carbon-supported Ni3B nanoparticles as catalysts for hydrogen generation from hydrolysis of ammonia borane

We report the preparation of Ni₃B and carbon-supported Ni₃B (denoted as Ni₃B/C) nanoparticles, and their catalytic performance for hydrogen generation from hydrolytic dehydrogenation of ammonia borane (NH₃BH₃, AB). Ni₃B and Ni₃B/C were prepared via a chemical reduction and crystallization in tetraethylene glycol solution. The obtained Ni₃B catalysts are in well-defined crystalline state and Ni₃B/C catalysts have a high dispersion in the carbon. The hydrogen generation measurement shows that the carbon-supported Ni₃B presents enhanced catalyst activity during hydrolytic dehydrogenation of AB. Among the as-prepared Ni₃B/C catalysts, Ni₃B/C with 34.25 wt% Ni₃B loading displays the best catalytic activity, delivering a high hydrogen release rate of 1168 mL min⁻¹ g⁻¹ and the lower activation energy of 46.27 kJ mol⁻¹. The kinetic results show that the hydrolysis is a first-order reaction in catalyst concentration, while it is a zero-order in AB concentration. Furthermore, the Ni₃B/C is a recyclable catalyst under mild reaction conditions, indicating that the carbon-supported Ni₃B is a promising catalyst for AB hydrolytic dehydrogenation.     

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.     

Alloyed palladium-nickel hollow nanospheres with interatomic charge polarization for improved hydrolytic dehydrogenation of ammonia borane

Hydrolysis reaction of ammonia borane (AB) has been considered as a safe and efficient hydrogen generation method, in which designing cost-effective and high-performance catalysts plays vital role. In this work, we have developed well dispersed palladium-nickel hollow nanospheres (PdNi HNSs) with tunable shell thickness and compositions via a facile galvanic replacement approach. The as-prepared PdNi HNSs show composition-dependent catalysis in the hydrolytic dehydrogenation of AB. The Pd₈₄Ni₁₆/C exhibiting sphere-shaped hollow interiors with average 70 nm particle size and 10 nm thin wall, presents the highest catalytic activity with the turnover frequency of 76.0 (mol H₂ min^?1 (mol Pd)^?1) and the activation energy of 33.5 kJ mol^?1. The superior catalytic effect of PdNi HNSs in enhancing hydrolysis efficiency of AB can be ascribed to two major factors: (1) high active surface areas of the unique hollow structure; (2) enhanced H adsorption attributed to the coupling between Pd and Ni induces polarization charges on Pd catalytic sites, which is indicated by the first-principles calculation and X-ray photoelectron spectroscopy studies. Furthermore, the catalysts exert good long-term recycling stability and catalytic activity for the hydrolytic dehydrogenation of AB. This work represents a strategy may hopefully be extended to synthesize other Pd-based hollow nanostructure with reduced Pd usage and increased catalytic active sites, and also sheds light on the exploration of utilizing interatomic interactions to regulate species adsorption/activation for highly efficient catalytic performance.     

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.     

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.     

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)).     

Strategic synthesis of graphene supported trimetallic Ag-based core–shell nanoparticles toward hydrolytic dehydrogenation of amine boranes

We reported the synthesis and characterization of two trimetallic (Ag@CoFe, and Ag@NiFe) core–shell nanoparticles (NPs), and their catalytic activity toward hydrolytic dehydrogenation of ammonia borane (AB) and methylamine borane (MeAB). The as-synthesized trimetallic core–shell NPs were obtained via a facile one-step in situ procedure using methylamine borane as a reducing agent and graphene as the support under ambient condition. The as-synthesized NPs are well dispersed on graphene, and exhibit higher catalytic activity than the catalysts with other conventional supports, such as the SiO₂, carbon black, and γ-Al₂O₃. Additionally, compared with NaBH₄ and AB, the as-synthesized Ag@CoFe/graphene NPs reduced by MeAB exhibit the highest catalytic activity, with the turnover frequency (TOF) value of 82.9 (mol H₂ min⁻¹ (mol Ag)⁻¹), and the activation energy (E_a) value of 32.79 kJ/mol. Furthermore, the as-prepared NPs exert good durable and magnetically recyclability for the hydrolytic dehydrogenation of AB and MeAB. Moreover, this simple strategic synthesis method can be easily extended to the facile preparation of other graphene supported multi-metal core–shell NPs.     

Bamboo fungus-derived magnetic porous carbon encapsulated nickel stabilized Rh nanoparticles as efficient catalysts for hydrolytic dehydrogenation of ammonia borane

Biomass-derived porous carbons are generally used as supports for metal nanoparticle (NP) stabilizations, while the strong hydrophilicity of such materials makes the as-prepared catalysts hard to be isolated after reaction, significantly affecting their potential applications. Herein, magnetic N-functionalized carbon (CN) encapsulated Ni composite (Ni@CN) prepared via pyrolysis of bamboo fungus pre-absorbed with nickel nitrate is exploited as a matrix to synthesize Rh/Ni@CN hybrid, which can be used as a magnetically recoverable catalytic material for hydrolytic dehydrogenation of ammonia borane (AB) to generate hydrogen. The Rh/Ni@CN (Rh loading: 0.84 wt%) exhibits an optimal activity (turnover frequency: 351 min⁻¹) for hydrogen evolution from hydrolytic dehydrogenation of AB. Most importantly, this catalyst can be simply isolated by a magnet and reused at least five times with complete conversion of AB to hydrogen. The strong interaction between the two metals and the small size of Rh NPs are responsible for the improved catalytic activity for hydrolytic dehydrogenation of AB. This work provides an eco-friendly and efficient strategy to fabricate excellent catalysts in catalytic applications.     

Ruthenium supported on nitrogen-doped porous carbon for catalytic hydrogen generation from NH3BH3 hydrolysis

In this paper, ruthenium supported on nitrogen-doped porous carbon (Ru/NPC) catalyst is synthesized by a simple method of in situ reduction using ammonia borane (AB) as reducing agent. The composition and structure of Ru/NPC catalyst are systematically characterized. This catalyst can efficiently catalyze the hydrolysis of AB. The hydrogen production reaction is completed within about 90 s at a temperature of 298 K and the maximum rate of hydrogen production is 3276 ml·s⁻¹·g⁻¹ with a reduced activation energy of 24.95 kJ·mol⁻¹. The turnover frequency (TOF) for hydrogen production is about 813 mol_H2·mol_Ru⁻¹·min⁻¹. Moreover, this catalyst can be recycled with a well-maintained performance. After five cycles, the maximum rate of hydrogen generation is maintained at 2206 ml·s⁻¹·g⁻¹, corresponding to 67.3% of the initial catalytic activity. Our results suggest that Ru/NPC prepared by in situ reduction is a highly efficient catalyst for hydrolytic dehydrogenation of AB.     

Visible-light-enhanced catalytic hydrolysis of ammonia borane using RuP2 quantum dots supported by graphitic carbon nitride

Hydrolytic dehydrogenation of ammonia borane (AB) driven by efficient catalysts has attracted considerable attention and is regarded as a promising strategy for hydrogen generation. Herein, RuP₂ quantum dots supported on graphitic carbon nitride (g-C₃N₄) were successfully prepared by in-situ phosphorization, yielding a highly efficient photocatalyst toward AB hydrolysis. The catalysts were characterized by field-emission scanning electron microscopy, transmission electron microscopy, x-ray diffraction, x-ray photoelectron microscopy, inductively coupled plasma atomic emission spectroscopy, UV–visible diffuse reflectance spectroscopy and photoluminescence spectroscopy. A conventional water-displacement method was employed to record the hydrogen volume as a function of reaction time. Owing to visible-light irradiation, the initial turnover frequency of the AB hydrolysis was significantly enhanced by 110% (i.e., 134 min^?1) at room temperature. Furthermore, the apparent activation energy decreased from 67.7 ± 0.9 to 47.6 ± 1.0 kJ mol^?1. The photocatalytic hydrolysis mechanism and catalyst reusability were also investigated.     

Acid site introduced by Al3+penta and boron in Pt/Al2O3 catalyst for dehydrogenation of methylcyclohexane

A series of catalysts with different acid strengths were obtained by constructing unsaturated pentacoordinate (Al³⁺_penta) sites in Al₂O₃ and loading with boron. The effects of support properties and the addition of boron on the strength and type of catalyst acid were investigated, and their influence on the dehydrogenation performance of methylcyclohexane (MCH) was discussed. In Pt-B/Al₂O₃-600 catalysts containing Al³⁺_penta sites, the strongly acidic L acid sites gradually decreased and the weakly acidic [L + B] acid sites gradually increased with increasing boron loading, indicating coverage of the Al³⁺_penta site by boron. In Pt-B/Al₂O₃-750 catalysts without Al³⁺_penta sites, strongly acidic L acid sites gradually decrease with increasing boron loading and weakly acidic [L + B] acid sites remains essentially unchanged. For Pt-B/Al₂O₃-600 catalysts, the effect of boron on the interaction of Pt with Al₂O₃ is minimized when the loading of boron is between 0 and 1 wt% and the MCH dehydrogenation performance increases with the number of weak acid sites. At a boron loading of 1 wt%, the abundance of weak acid sites maintains the dispersion of Pt and allows a suitable interaction between Pt and Al₂O₃, thus enhancing the dehydrogenation performance of MCH.     

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.     

Sulphur and nitrogen-doped metal-free microalgal carbon catalysts for very active dehydrogenation of sodium borohydride in methanol

Micro algae based on Spirulina platensis is successfully used for the synthesis of S and N-doped metal-free carbon materials. The procedure consists of three stages; (i) Activated carbon production by KOH activation in CO₂ atmosphere (S-AC), (ii) S atom doping to the obtained S-AC using sulphuric acid by hydrothermal activation (S-AC-S), (iii) N atom doping by hydrothermal activation to S-AC obtained using nitric acid (S-AC-S-N). The S and N doped metal-free catalysts are used for H₂ release in NaBH₄ methanolysis reaction (NaBH₄-MR) for the first time. The metal-free carbon catalysts are characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM-EDS), X-ray diffractometer spectroscopy (XRD), Fourier-transform infrared spectroscopy (FTIR), nitrogen adsorption and elemental analysis (CHNS) methods. When the HGR values obtained for S-AC-S-N (26,000 mL min^?1 g^?1) and S-AC (2641 mL min^?1 g^?1) are compared, there is a 9.84-fold increase. Activation energy (Ea) value for S-AC-S-N was 10.59 kJ mol^?1.