CuO–NiO/Co3O4 hybrid nanoplates as highly active catalyst for ammonia borane hydrolysis

Dehydrogenation of hydrogen-rich chemicals, such as ammonia borane (AB), is a promising way to produce hydrogen for mobile fuel cell power systems. However, the practical application has been impeded due to the high cost and scarcity of the catalysts. Herein, a low-cost and high-performing core-shell structured CuO–NiO/Co₃O₄ hybrid nanoplate catalytic material has been developed for the hydrolysis of AB. The obtained hybrid catalyst exhibits a high catalytic activity towards the hydrolysis of AB with a turnover frequency (TOF) of 79.1 mol_H2 mol cat⁻¹ min⁻¹. The apparent activation energy of AB hydrolysis on CuO–NiO/Co₃O₄ is calculated to be 23.7 kJ.mol⁻¹. The synergistic effect between CuO–NiO and Co₃O₄ plays an important role in the improvement of the catalytic performance. The development of this high-performing and low-cost CuO–NiO/Co₃O₄ hybrid catalytic material can make practical applications of AB hydrolysis at large-scale possible.     

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

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

Performance evaluation of hydrogen generation system with electroless-deposited Co–P/Ni foam catalyst for NaBH4 hydrolysis

In this work, the performance of a hydrogen generation system with an electroless-deposited Co–P/Ni foam catalyst for NaBH₄ hydrolysis was evaluated. The performance of a hydrogen generator using a combination of Co/γ-Al₂O₃ and Co–P/Ni foam catalysts was also evaluated in order to address the shortcomings with the individual catalysts. The generator had high conversion efficiency, fast response characteristics, and strong catalyst durability. Hydrogen generation tests were performed to investigate the effect of the composition of the NaBH₄ solution on the hydrogen generation properties. The generator's conversion efficiency decreased with an increase in the amount of solute dissolved in NaBH₄ solution because of the accumulation of precipitates on the catalyst, and NaOH concentration had a greater effect on the hydrogen generation properties than did NaBH₄ concentration. According to these results, the hydrogen generation system with the Co–P/Ni foam catalyst is suitable as a hydrogen supplier for proton exchange membrane fuel cells owing to the strong durability and inexpensive cost of the catalyst.     

Efficient catalytic properties of Co–Ni–P–B catalyst powders for hydrogen generation by hydrolysis of alkaline solution of NaBH4

The aim of the present work is to study the catalytic efficiency of amorphous Co–Ni–P–B catalyst powders in hydrogen generation by hydrolysis of alkaline sodium borohydride (NaBH₄). These catalyst powders have been synthesized by chemical reduction of cobalt and nickel salt at room temperature. The Co–Ni–P–B amorphous powder showed the highest hydrogen generation rate as compared to Co–B, Co–Ni–B, and Co–P–B catalyst powders. To understand the enhanced efficiency, the role of each chemical element in Co–Ni–P–B catalyst has been investigated by varying the B/P and Co/Ni molar ratio in the analyzed powders. The highest activity of the Co–Ni–P–B powder catalyst is mostly attributed to synergic effects caused by each chemical element in the catalyst when mixed in well defined proportion (molar ratio of B/P = 2.5 and of Co/(Co + Ni) = 0.85). Heat-treatment at 573 K in Ar atmosphere causes a decrease in hydrogen generation rate that we attributed to partial Co crystallization in the Co–Ni–P–B powder. The synergic effects previously observed with Co–Ni–B and Co–P–B, now act in a combined form in Co–Ni–P–B catalyst powder to lower the activation energy (29 kJ mol⁻¹) for hydrolysis of NaBH₄.     

Room temperature hydrogen generation from hydrolysis of ammonia–borane over an efficient NiAgPd/C catalyst

NiAgPd nanoparticles are successfully synthesized by in-situ reduction of Ni, Ag and Pd salts on the surface of carbon. Their catalytic activity was examined in ammonia borane (NH₃BH₃) hydrolysis to generate hydrogen gas. This nanomaterial exhibits a higher catalytic activity than those of monometallic and bimetallic counterparts and a stoichiometric amount of hydrogen was produced at a high generation rate. Hydrogen production rates were investigated in different concentrations of NH₃BH₃ solutions, including in the borates saturated solution, showing little influence of the concentrations on the reaction rates. The hydrogen production rate can reach 3.6–3.8 mol H₂ mol_cat⁻¹ min⁻¹ at room temperature (21 °C). The activation energy and TOF value are 38.36 kJ/mol and 93.8 mol H₂ mol_cat⁻¹ min⁻¹, respectively, comparable to those of Pt based catalysts. This nanomaterial catalyst also exhibits excellent chemical stability, and no significant morphology change was observed from TEM after the reaction. Using this catalyst for continuously hydrogen generation, the hydrogen production rate can be kept after generating 6.2 L hydrogen with over 10,000 turnovers and a TOF value of 90.3 mol H₂ mol_cat⁻¹ min⁻¹.     

Hydrogen generation from hydrolysis of NH3BH3 by an electroplated Co–P catalyst

This paper investigates the effect of an electroplated Co–P catalyst on hydrogen generation kinetics from hydrolysis of NH₃BH₃. The Co–P catalyst is composed of an amorphous Co–P phase and Co nanoparticles. An increase in NH₃BH₃ concentration caused the hydrogen generation rate to increase dramatically. The Co–P catalyst shows a large hydrogen generation rate for 2 wt% NH₃BH₃ solution at 30 °C. This is 1.8 times higher than that of the Pt/C catalysts and 6 times higher than that of Ru catalysts. The activation energy for hydrolysis of NH₃BH₃ by the Co–P catalyst is calculated to be 22 kJ/mol, which is close to that of noble metal-based catalysts.     

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

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

Graphene supported Pt–Ni bimetallic nanoparticles for efficient hydrogen generation from KBH4/NH3BH3 hydrolysis

Developing highly efficient and stable supported bimetallic nanoparticles catalysts via a facile strategy is one of the most admirable methods for sustainable hydrogen production from borohydride hydrolysis. Herein, we developed a facile technology for rapidly and straightforwardly manufacturing Pt–Ni bimetallic nanoparticles (BNPs) supported by partially reduced graphene oxide (prGO) with excellent catalytic activity and outstanding durability for hydrogen production from KBH₄ and NH₃BH₃ alkaline solution. The uniformly dispersed Pt₄₀–Ni₆₀ BNPs with a statistical size of around 2.6 nm exhibited a surprising catalytic activity of 23,460 mol-H₂·h^?1·mol-Pt^?1 at 308 K, moreover, whose activity was high up to 80% of the first time even after 30 runs, demonstrating an outstanding stability. The apparent activation energy for dehydrogenation of KBH₄ and NH₃BH₃ were respectively about 27.8 and 33.6 kJ/mol for the prepared Pt₄₀–Ni₆₀/prGO catalyst. The extraordinary catalytic activity of the Pt₄₀–Ni₆₀/prGO catalyst owing to the strong charge transfer effect between Pt–Ni BNPs and graphene.     

Improved hydrogen production performance of Ni–Al2O3/CaO–CaZrO3 composite catalyst for CO2 sorption enhanced CH4/H2O reforming

Bifunctional composite catalysts are very intrigued to produce hydrogen via CO₂ sorption enhanced CH₄/H₂O reforming. However, their hydrogen production performance declined over multiple cycles, owing to the structure collapse and the sintering of active component under high-temperature regeneration. This work reported the facile synthesis of long-lasting Ni–Al₂O₃/CaO–CaZrO₃ composite catalysts with less inert components (36 wt%) for stable hydrogen production over the multiple cycles of CO₂ sorption enhanced CH₄/H₂O reforming. The effects of reaction and regeneration temperature on the hydrogen production performance of Ni–Al₂O₃/CaO–CaZrO₃ were explored. Ni–Al₂O₃/CaO–CaZrO₃ demonstrated high activity and stability while fixing reaction temperature as 600 °C and regeneration temperature as 750 °C. Of particular importance, H₂ concentration was 98 vol% even after 10 hydrogen production cycles due to the inert component CaZrO₃ having a cross-linked structure. The distribution of CaZrO₃ in the composite as a coral-like structure inhibited the sintering of CaO through high Taman temperature and physical separation. Moreover, it provided the skeleton support and pore volume for the repeated expansion and contraction process of CaO to CaCO₃ during the cycling process. Finally, the sintering of Ni slowed down in appropriate regeneration temperature to maintain the structure of the composite catalyst, which further improved the catalyst's stability over multiple cycles.     

Optimization for hydrogen production from methanol partial oxidation over Ni–Cu/Al2O3 catalyst under sprays

In this work, a novel Ni–Cu/Al₂O₃ catalyst is used to trigger the partial oxidation of methanol (POM) for hydrogen production. This reaction system also employed ultrasonic sprays to aid in dispersing methanol fuel. The prepared catalyst is analyzed by scanning electron microscope (SEM), energy-dispersive X-ray (EDX) spectroscopy, and X-ray diffraction (XRD) to explore the catalyst's surface structure, elemental composition, and physical structure, respectively. The Box-Behnken design (BBD) of response surface methodology (RSM) is utilized for experimental design to achieve process optimization. The operating parameters comprise the O₂/C molar ratio (0.5–0.7), preheating temperature (150–250 °C), and weight percent (wt%) of Ni (10–30%) in the catalyst. The results show that methanol conversion is 100% in all the operating conditions, while the reaction temperature for H₂ production ranges from 160 to 750 °C, stemming from heat released by POM. The significance and suitability of operating conditions are also analyzed by analysis of variance (ANOVA). It indicates that the highest H₂ yield is 2 mol (mol CH₃OH)^?1, occurring at O₂/C = 0.5, preheating temperature = 150 °C, and Ni wt% = 10. Compared with the commercial h-BN-Pt/Al₂O₃ catalyst, the prepared Ni–Cu/Al₂O₃ catalysts have higher activity for H₂ production. The O₂/C ratio is the most influential factor in the H₂ yield. Moreover, the interaction of the O₂/C ratio and Ni content is sound, reflecting that changing Ni content in the catalyst will affect the trend of H₂ yield under each O₂/C.     

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

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

Superhydrophobic Pt–Pd/Al2O3 catalyst coating for hydrogen mitigation system of nuclear power plant

Passive auto-catalytic recombiner (PAR) system is an important hydrogen mitigation method which has been applied in most modern light water nuclear reactors. The two challenges for the highly efficient PAR are the detrimental effect of water and poisoning by fission products. In this study, to address the two challenges, superhydrophobic Pt–Pd/Al₂O₃ catalyst coatings were prepared by wet impregnation method and the grafting of 1H,1H,2H,2H-perfluorooctyltriethoxysilane.The formation of a Pt–Pd intermetallic compound was confirmed by in situ diffuse reflectance infrared Fourier transform infrared spectroscopy for the Pt–Pd/Al₂O₃ catalyst. The Pt–Pd/Al₂O₃ catalyst exhibited a superior resistance of water poisoning to the monometallic catalysts. In addition, compared with the monometallic catalysts, the least influence by the iodine poisoning was observed for the Pt–Pd/Al₂O₃ catalyst, which is attributed to the smallest influence on the bindings of H₂ and O₂ on the Pt–Pd intermetallic compound by the iodine addition. For the reactor with the superhydrophobic Pt–Pd/Al₂O₃ catalyst coating, under the conditions simulating the nuclear accident, the reaction was ignited immediately as soon as the hydrogen was introduced at 298 K and the hydrogen conversion kept 100% when the reaction temperature exceeded 398 K. The superhydrophobic Pt–Pd/Al₂O₃ catalyst coating showed great potential for the mitigation of hydrogen containing various poisons during the nuclear accident.     

Ammonia decomposition over SiO2-supported Ni–Co bimetallic catalyst for COx-free hydrogen generation

NH₃ decomposition over non-noble catalyst to generate CO_x-free H₂ has attracted great attention in recent years. In this work, fumed SiO₂-supported Ni, Co and Ni–Co bimetallic catalysts are synthesized by using a co-impregnation method and evaluated for NH₃ decomposition, which shows that the bimetallic catalysts exhibit better catalytic activity than the monometallic ones. This enhanced activity observed on bimetallic catalyst can be largely attributed to the more appropriate catalyst metal-N binding energy resulting from the synergistic effect between Ni and Co in the formed Ni–Co alloy. Among the synthesized catalysts, Ni₅Co₅/SiO₂ synthesized with the Ni/Co molar ratio of 5:5 achieves 76.8% NH₃ conversion under a GHSV of 30,000 mL h⁻¹ g⁻¹_cat at 550 °C and shows the best catalytic activity, which can be further improved by doping with K (78.1% NH₃ conversion at 30,000 mL h⁻¹ g⁻¹_cat), and the obtained Ni₅Co₅/SiO₂–K also shows excellent catalytic stability.     

Electroless-deposited Co–P catalysts for hydrogen generation from alkaline NaBH4 solution

Cobalt–phosphorus (Co–P) catalysts, which were electroless deposited on Cu sheet, have been investigated for hydrogen generation from alkaline NaBH₄ solution. The microstructures of the as-prepared Co–P catalysts and their catalytic activities for hydrolysis of NaBH₄ are analyzed in relation to pH value, NaH₂PO₂ concentration, and the deposition time. Experimental results show that the Co–P catalyst formed in the bath solution with pH value of 12.5, NaH₂PO₂ concentration of 0.8 M, and the deposition time no more than 6 min presents the highest hydrogen generation rate of 1846 mL min⁻¹ g⁻¹. Furthermore, the as-prepared catalyst also shows good cycling capability and the corresponding activation energy is calculated to be 48.1 kJ mol⁻¹. The favorable catalytic performance of the electroless-deposited Co–P catalysts indicates their potential application for quick hydrogen generation from hydrolysis of NaBH₄ solution.     

Hydrogen generation from alkaline NaBH4 solution using a dandelion-like Co–Mo–B catalyst supported on carbon cloth

In this study, a dandelion-like Co–Mo–B catalyst was prepared on carbon cloth (CC) by two-step electrodeposition method for the first time. The composition and microscopy are characterized by XRD and SEM technology. The results revealed that the as-synthesized Co–Mo–B catalyst exhibited high hydrogen generation rate (1280.80 mL min^?1 g^?1) and low activation energy (51.0 kJ mol^?1) for the hydrolysis of alkaline NaBH₄ solution. The results reveal that the reason might be due to high specific surface of the novel dandelion-like nanostructure and the synergistic effect of Co, Mo and B. Moreover, the catalytic activity was closely related to NaOH concentration, and OH^– anions were competitive with BH₄^– anions in alkaline NaBH₄ solution to transfer to the catalyst surface.     

Optimization of hydrogen generation process from the hydrolysis of activated Al–NaCl–SiC composites using Taguchi method

Novel Al–NaCl–SiC composites for hydrogen generation were prepared by mechanical ball milling. NaCl is a well-known salt for the activation of Al. SiC, which is much harder and more rigid than NaCl, was added as a milling aid. In this optimization study Taguchi method was used for design of experiments. In the experimental design using the L16 (4 ? 3) orthogonal array, 4-levels of NaCl and SiC ratios and mechanical milling times were used. Confirmation tests were carried out for the optimum levels determined by Taguchi method. An analysis of variance was performed to determine the relative importance of the control factors and their contribution to the performance characteristic. It was found that NaCl has the greatest effect on hydrogen generation performance, followed by mechanical milling time and SiC ratio. The highest values of these parameters were determined as optimum levels for maximum hydrogen generation. X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive spectroscopy (EDS) analyzes were performed to investigate the relation between hydrogen generation performance and morphology of milled powders. The grain (crystal) dimensions of some milled powders were calculated from the XRD data using the Scherrer equation. Grain refinement, reduction in grain size during mechanical milling was used as a measure of the severity of plastic deformation. It was observed that the grain sizes were reduced to a few tens of nanometers with the ball milling process.     

Enhancement of hydrogen energy from Casuarina equisetifolia using NiO–Pr2O3/TiO2 and NiO/TiO2 nano composites

Hydrogen is the eco friendly fuel that can supplement the requirements for power generation.Nickel based nano composites attracted much researchers due to its wide applications in various fields viz., solar cells, capacitors, batteries and aerospace engineering. NiO-Pr₂O₃/TiO₂ and NiO/TiO₂ nano composites have high catalytic activity for producer gas conversion by the process of decomposition of tar molecules generated during biomass gasification. In this work, we have investigated the growth of NiO-Pr₂O₃/TiO₂ and NiO/TiO₂ nano composites by the method of deposition precipitation technique. Structural investigation represented that the TiO₂ possess cubic structure with preferential orientation along (111) plane. Morphological features denoted the formation of non agglomerated grains. The sizes of the grains with nanometer scale have been identified by transmission electron microscopy. The surface area and porosity nature of the nano composites has been analyzed using Branauer Elmer Teller and Barrett-Joyner - Halenda techniques, respectively. The estimated value of surface area is found to be 110 and 81 m²g^-1 for NiO-Pr₂O₃/TiO₂ and NiO/TiO₂ nano composites, respectively. The increment in the content of hydrogen present in the producer gas has been investigated using catalytic tar cracking method. The NiO-Pr₂O₃/TiO₂ nano composite exhibited better tar cracking with higher content of hydrogen conversion than NiO/TiO₂.     

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.     

The effects of plasma treatment on electrochemical activity of Co–W–B catalyst for hydrogen production by hydrolysis of NaBH4

A plasma treatment of Co–W–B catalyst increases the rate of hydrogen generation from the hydrolysis of NaBH₄. The catalytic properties of Co–W–B prepared in the presence of plasma have been investigated as a function of NaBH₄ concentration, NaOH concentration, temperature, plasma applying time, catalyst amount and plasma gases. The Co–W–B catalyst prepared with cold plasma effect hydrolysis in only 12 min, where as the Co–W–B catalyst prepared in known method with no plasma treatment in 23 min. The activation energy for first-order reaction is found to be 29.12 kJ mol⁻¹.     

Ultrafine cobalt–molybdenum–boron nanocatalyst for enhanced hydrogen generation property from the hydrolysis of ammonia borane

The hydrolysis of ammonia borane (NH₃BH₃) is recognized as an efficient way of hydrogen generation if it can be effectively catalyzed. In this work, a series of cobalt–molybdenum–boron (Co–Mo–B) nanoparticles (NPs) on copper (Cu) foil are introduced as catalysts for NH₃BH₃ hydrolysis by electroless deposition method. The influence of the depositing pH value on the catalytic property is investigated by adjusting the pH value ranged from 10.5 to 12.0. By optimizing the value to 11, the ultrafine Co–Mo–B NPs with the grain size around 4.3 nm show the best catalytic property for NH₃BH₃ hydrolysis. The hydrogen generation rate reaches 5818.0 mL·min⁻¹·g⁻¹ when the hydrolysis temperature is 298 K. The thermodynamic tests show that the lower activation energy (E_a) is estimated to be 59.3 kJ·mol⁻¹. It can be found that the catalytic property in this work overtakes that of partial non-precious metal NPs, and is even better than some precious metal NPs previously reported. The hydrolysis reaction of NH₃BH₃ catalyzed by ultrafine Co–Mo–B NPs is a non-spontaneous process. In addition, the cycling ability of the ultrafine Co–Mo–B NPs is also studied and the results demonstrate that the catalyst is a recyclable one toward the hydrolysis of NH₃BH₃ under mild reaction conditions.