Hollow Ni-SiO2 nanosphere-catalyzed hydrolytic dehydrogenation of ammonia borane for chemical hydrogen storage

Nickel clusters contained within silica nanospheres (20-30 nm) were synthesized by using a Ni(NH₃)₆Cl₂ crystal template method in a polyoxyethylene-nonylphenyl ether/cyclohexane reversed micelle system followed by an in situ reduction in aqueous NaBH₄/NH₃BH₃ solutions. Metallic nickel clusters exist inside the SiO₂ nanospheres prepared by the method while oxidized nickel clusters prepared by the conventional impregnation method were supported on the outer surface of silica as shown in the results of transmission electron microscope (TEM)/energy dispersive X-ray (EDX) and X-ray photoelectron spectroscopy (XPS) measurements. The nickel clusters inside of silica nanospheres show higher catalytic activity for hydrolysis of ammonia borane to generate stoichiometric amount of hydrogen than the supported nickel catalysts.     

Tuning catalytic performances of cobalt catalysts for clean hydrogen generation via variation of the type of carbon support and catalyst post-treatment temperature

Multi-walled carbon nanotubes, three types of activated carbons, single wall carbon nanotube and reduced graphene oxides were used to synthesize nano-sized Co catalysts for H₂ preparation via NH₃ decomposition. Catalyst samples were characterized by number of techniques such as N₂ physisorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopes (XPS), Transmission electron microscopy (TEM), CO chemisorption, temperature-programmed reduction (H₂-TPR) and temperature-programmed desorption (N₂-TPD). The catalytic activities of the studied catalysts for H₂ production via NH₃ decomposition were measured in a fixed-bed micro-reactor. Co catalyst supported on multi-wall carbon nanotubes has shown the highest catalytic activity. The Co particles size was significantly affected by the variation of the post-treatment temperature. The Co particles size in the range of 4.7–64.8 nm can be effectively controlled by varying post-treatment temperature between 230 and 700 °C. The maximum TOF of NH₃ decomposition was registered on cobalt catalyst post-treated at 600 °C.     

Hierarchical Fe-ZSM-5 with nano-single-unit-cell for removal of nitrogen oxides

Nano-single-unit-cell hierarchical Fe-ZSM-5 (designated NSUCH Fe-ZSM-5) was successfully synthesized and characterized by X-ray diffraction, scanning electron microscope, transmission electron micrographs, inductive coupled plasma emission spectrometer, and X-ray photoelectron spectroscopy techniques. NSUCH Fe-ZSM-5 exhibits great lamellar crystal structure and Fe species are present in the form of crystalline γ-Fe₂O₃. Most of the Fe species got into mesoporous zeolite channels, presenting in a well-dispersed state. The adsorbed oxygen on an external surface is a benefit for the NH₃-NO selective catalytic reduction reaction. The catalytic behaviors for removal of nitrogen oxides reveal that NSUCH Fe-ZSM-5 displays better activity than conventional Fe-ZSM-5 during the temperatures of 250–400°C.     

Non-noble metallic nanoparticles supported on titania spheres as catalysts for hydrogen generation from hydrolysis of ammonia borane under ultraviolet light irradiation

Herein, a report on non-noble metal (Ni, Co, Cu, and their combination) nanoparticles (NPs) supported on TiO₂ spheres as catalysts for hydrogen generation via hydrolysis of ammonia borane (NH₃BH₃, AB) is provided. The TiO₂ spheres were prepared through a template method by using polystyrene (PS). The metallic nanoparticles were synthesized by a redox replacement reaction. The structure, morphology, and chemical composition of the obtained samples were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) equipped with energy dispersive X-ray spectroscopy (EDX), and X-ray Photoelectron Spectroscopy (XPS). The characterization results showed that the metallic nanoparticles were well dispersed on the TiO₂ supports. The catalytic activity toward the hydrolysis of AB was found to correlate well with the amount of metallic elements in catalysts while for the multicomponent phases, a synergistic effect was noticed. Theoretical calculations revealed that Ni, Co, and Cu atoms significantly influenced the electronic behavior of TiO₂ and thereby, the catalytic properties of the materials.     

Catalytic activities of non-noble metals for hydrogen generation from aqueous ammonia–borane at room temperature

We have studied catalytic performance of supported non-noble metals for hydrogen generation from aqueous NH₃BH₃ at room temperature. Among the tested non-noble metals, supported Co, Ni and Cu are the most catalytically active, with which hydrogen is released with an almost stoichiometric amount from aqueous NH₃BH₃, whereas supported Fe is catalytically inactive for this reaction. Support effects on the catalytic activity have been investigated by testing the hydrogen generation reaction in the presence of Co supported on γ-Al₂O₃, SiO₂ and C and it is found that the Co/C catalyst has higher activity. Activation energy for hydrogen generation from aqueous NH₃BH₃ in the presence of Co/γ-Al₂O₃ was measured to be 62 kJ mol⁻¹; this may correspond to the step of BN bond breaking. Particle size, surface morphology and surface area of the supported metal catalysts were examined by X-ray diffraction (XRD), transmission electron microscope (TEM), energy dispersive X-ray (EDX) and BET experiments. It is found that with decreasing the particle size the activity of the supported catalyst is increased. The low-cost and high-performance supported non-noble metal catalysts may have high potential to find its application to the hydrogen generation for portable fuel cells.     

Effect of the amine group content on catalytic activity and stability of mesoporous silica supported Pd catalysts for additive-free formic acid dehydrogenation at room temperature

A strong metal-support interaction (SMSI) between amine-functionalized silica supports and Pd nanoparticles is one of important factors to determine the catalytic activity of additive-free formic acid dehydrogenation at room temperature over Pd/NH₂-silica catalysts. However, there are few reports on the effect of the content of amine functional groups on the SMSI and catalytic performance for formic acid dehydrogenation. In this study, we tried to maximize the content of amino-propyl groups on the surface of mesoporous silica supports (KIE-6) via hydroxylation of KIE-6 surface before amine functionalization and investigated the effect of the content of amine functional groups on the catalytic activity and stability for formic acid dehydrogenation. As a result, Pd/NH₂-hydroxylated KIE-6 (Pd/NH₂-OH-KIE-6) catalysts with more amine functional groups provided higher initial catalytic activity (595 mol H₂ mol catalyst⁻¹h⁻¹) than Pd/NH₂-KIE-6 catalysts. However, Pd/NH₂-KIE-6 catalysts showed higher catalytic stability in comparison with Pd/NH₂-OH-KIE-6 catalysts. After various characterizations of catalysts, it was demonstrated that the enhanced initial catalytic activity of Pd/NH₂-OH-KIE-6 catalysts is attributed to the higher ratio of Pd/PdO derived from the increased content of amine groups of NH₂-OH-KIE-6 supports. In contrast, the low surface area of NH₂-OH-KIE-6 promoted the aggregation of Pd nanoparticles on Pd/NH₂-OH-KIE-6 catalysts, which resulted in the lower catalytic stability of Pd/NH₂-OH-KIE-6 catalysts than Pd/NH₂-KIE-6 catalysts. Thus it was concluded that confinement of Pd nanoparticles to the pores of supports is a more dominant factor to achieve higher catalytic stability, while the initial catalytic activity is affected by the electronic state of Pd nanoparticle determined by the content of amine functional groups on the surface of supports.     

Improved catalytic performance of metal oxide catalysts fabricated with electrospinning in ammonia borane methanolysis for hydrogen production

Electrospun Ni and Cu metal oxide catalysts are successfully synthesized through electrospinning and conventional sol-gel methods to show advantages of electrospinning on catalytic performance in ammonia borane (NH₃BH₃) methanolysis for hydrogen production. An experimental assessment is presented by the characterization of interior and exterior properties of all catalysts and their catalytic activity towards NH₃BH₃ methanolysis. The systematic studies are performed in order to figure out of kinetic interpretation. Catalytic NH₃BH₃ methanolysis reactions are carried out at different catalyst amounts (5–15 mg), initial NH₃BH₃ concentrations (0.36–6.0 M) and temperatures (20–50 °C). Thanks to the higher pore volume/S_BET ratio, fiber type nanostructured Cu oxide catalyst exhibits the highest catalytic activity compared with sol-gel prepared ones. The results of kinetic studies show that the fiber type Cu oxide catalyst catalyzed methanolysis of NH₃BH₃ and follows the first order reaction kinetic model with 35 kJ mol⁻¹ activation energy value.     

Influence of CeO2 morphology on WO3/CeO2 catalyzed NO selective catalytic reduction by NH3

WO₃/CeO₂ catalysts with different support morphologies were fabricated by incipient wetness technique and applied to selective catalytic reduction of NO by NH₃ (NH₃-SCR). WO₃/CeO₂ rod (WCR) displayed higher catalytic activity and resistance to SO₂ and H₂O compared with WO₃/CeO₂ polyhedron (WCP) and WO₃/CeO₂ cube (WCC). N₂-BET, XRD, Raman, H₂-TPR, TEM, HRTEM, NH₃-TPD, XPS and in situ DRIFTS were conducted to investigate the physicochemical properties of the catalysts and the adsorption of NH₃ and NO_x species on the catalytic surface. These characterization results demonstrated that the larger BET surface area, the smaller CeO₂ particle size, the higher surface acidity, the more oxygen defects, the better redox performance, and the higher Ce³⁺ and O_α ratios of the catalysts played critical functions in obtaining more outstanding NH₃-SCR catalytic performance. All of these characterization results were also closely related to the CeO₂ morphology. The results of the in situ DRIFTS showed that the WCR had the highest intensities of the adsorbed NO_x and NH₃ species among these three catalysts. The reactions between adsorbed species attributed to NO_x and NH₃ on the catalyst surface can also be a key factor in the NH₃-SCR catalytic performance enhancement.     

Enhanced methanol oxidation on PtNi nanoparticles supported on silane-modified reduced graphene oxide

Developing low cost, highly efficient, and long-term stability electrocatalysts are critical for direct oxidation methanol fuel cell. Despite huge efforts, designing low-cost electrocatalysts with high activity and long-term durability remains a significant technical challenge. Here, we prepared a new kind of platinum-nickel catalyst supported on silane-modified graphene oxide (NH₂-rGO) by a two-step method at room temperature. Powder X-ray diffraction, UV–vis spectroscopy, Raman, FTIR spectroscopy and X-ray photoelectron spectroscopy results confirm that GO was successfully modified with 3-aminopropyltriethoxysilane (APTES), which helps to uniformly disperse PtNi nanoparticles. Cyclic voltammetry, chronoamperometry, CO-stripping and rotating disk electrode (RDE) results imply that PtNi/NH₂-rGO catalyst has significantly higher catalytic activity, enhance the CO toxicity resistance, higher stability and much faster kinetics of methanol oxidation than commercial Pt/C under alkaline conditions.     

Magnetic dendritic KCC-1 nanosphere-supported cobalt composite as a separable catalyst for hydrogen generation from NaBH4 hydrolysis

The introduction of magnetism into a catalyst can greatly optimize its separation performance. In the present work, a kind of magnetically separable catalysts for promoting NaBH₄ hydrolysis have been fabricated by anchoring cobalt nanoparticles on magnetic dendritic KCC-1 nanospheres composed of magnetic Fe₃O₄ core and fibrous shell. The fabricated catalysts were characterized with various characterization methods, including absorption spectroscopy (AAS), scanning electron microscopy (SEM), high-resolution transmission electronic microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), vibrating sample magnetometry (VSM), and Fourier transform infrared (FT-IR), etc. This kind of catalysts exhibit high catalytic activity for promoting the hydrolysis of NaBH₄ under alkaline conditions, giving a hydrogen generation rate and activation energy of 3.83 L min⁻¹ g_Co⁻¹ (30 °C) and 53.63 kJ mol⁻¹, respectively. After used for 5 cycles, the catalyst showed 36.5% catalytic activity reserved. Most importantly, the magnetism of the catalyst made it easily separated and recycled from the solution after the reaction completed. The development of this kind of catalysts could provide a promising option for catalyzing NaBH₄ hydrolysis for portable hydrogen production from.     

Cost-effective Co3O4 nanospheres on nitrogen-doped graphene used as highly efficient catalyst for oxygen reduction reaction

Developing low-cost, efficient and stable catalyst for the oxygen reduction reaction is meaningful and necessary for the industrialization of fuel cells. In this work, we report the controllable synthesis of Co₃O₄ nanospheres uniformly anchored on N-doped reduced graphene oxide (N-rGO) sheets with significant catalytic activity for the oxygen reduction reaction via a simple two-step approach. Results show that there is an interaction between Co₃O₄ nanospheres and N-rGO after riveting on N-rGO, which is beneficial to the electron transfer between them. The Co₃O₄ NS/N-rGO hybrid has excellent catalytic activity, comparable to commercial Pt/C catalyst. The transferred electron number of the oxygen reduction reaction on Co₃O₄ NS/N-rGO is around 3.95. The hybrid has more excellent durability and methanol resistance than commercial Pt/C. The Co₃O₄ NS/N-rGO catalyst in our work provides a cost-effective the oxygen reduction reaction catalyst alternative to the precious metal Pt in fuel cell.     

Carbon nanotube-graphene hybrid supported platinum as an effective catalyst for hydrogen generation from hydrolysis of ammonia borane

In this study, we report the results of a kinetic study on the hydrogen (H₂) generation from the hydrolysis of ammonia borane (NH₃BH₃) catalyzed by Platinum supported on carbon nanotube-graphene hybrid material (Pt/CNT-G). Synthesized catalyst was characterized by TGA, XRD, CP-OES, TEM and SEM-EDX techniques. Characterization studies have shown that the CNT-G hybrid support material provides desired distribution of the Pt particles on the support material. The effect of various parameters such as catalyst loading, reaction temperature, effect of NaOH and the effect of NH₃BH₃ concentration are also determined. Experimental results showed that the Pt/CNT-G catalyst exhibited high catalytic activity on NH₃BH₃ hydrolysis reaction to release H₂. It has been found that Pt/CNT-G catalyst shows low activation energy of 35.34 kJ mol⁻¹ for hydrolysis reaction of NH₃BH₃. Pt/CNT-G catalyst also exhibited high catalytic activity with turnover frequency (TOF) of 135 (mol_H2/mol_cat.min). Therefore, the synthesized Pt/CNT-G catalyst is a potential candidate for enhanced H₂ generation through NH₃BH₃ hydrolysis.     

Effect of reaction conditions and surface characteristics of Ru/CeO2 on catalytic performance for ammonia synthesis as a clean fuel

The impact of reaction parameters and surface characteristics on NH₃ synthesis activity of the Ru/CeO₂ catalyst was explored. An exceptionally higher NH₃ synthesis activity was observed at 375 °C and 2.5 MPa gauge pressure. The H₂/N₂ ratio among the reactants strongly affected the catalytic activity. The catalytic activity enhanced at higher temperatures for a higher H₂/N₂ ratio, while the lower H₂/N₂ ratio was suitable for improved NH₃ synthesis at a lower temperature while working at 2.5 MPa gauge pressure. Likewise, NH₃ synthesis activity of Ru/CeO₂ catalyst enhanced abruptly on increasing pressure at relatively higher temperature conditions, using a reactant flow with a higher H₂/N₂ ratio. The NH₃ synthesis activity enhanced with time on stream. This increase in activity was associated with an increase in Ru particles with high dispersion on the surface of the catalyst during NH₃ synthesis, confirmed by FIB-TEM and EDS analysis of the cross-sections of catalyst particles.     

A comparative study of ZrO2, Y2O3 and Sm2O3 promoted Ni/SBA-15 catalysts for evaluation of CO2/methane reforming performance

Ni-based/SBA-15 catalysts, were promoted by 3wt % of samaria (Sm₂O₃), Yttria (Y₂O₃) and Zirconia (ZrO₂), by two-solvent impregnation method. The catalysts characterization was performed by N2 adsorption–desorption, X-ray Diffraction (XRD), X-ray Fluorescence (XRF), High Resolution Transmission Electron Microscopy (HRTEM), Field Emission Electron Scanning Microscopy (FESEM), Temperature Programmed Oxidation/Reduction (TPO/TPR) and NH₃-Temperature Programmed Desorption (NH₃-TPD) techniques. Then, evaluated by CO₂/methane reforming.The CO₂/methane reforming outcomes revealed that samaria-promoted catalyst showed excellent activity, stability and cock resistance, while yttria-promoted catalyst just illustrated good activity at high temperature and zirconia-promoted catalyst didn't show any modification in catalytic performance in comparison to Ni-based catalyst with no promoter. Samaria-promoted TEM and TPR analysis, indicated adding samaria improved the NiO particles interaction with SBA-15 support pores wall and NiO dispersion. The TPO analysis displayed that coke deposition in samaria-promoted sample after 12 h reaction is less than yttria-promoted during stream of 5 h. Also, it is suggested that for samaria containing catalyst, cock deposition occurred on the support. Therefore, nickel active sites were preserved for time on stream of 12 h, which is the main reason for samaria-promoted catalyst superior stability than other's.     

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.     

Carbon nanotubes supported PtPd hollow nanospheres for formic acid electrooxidation

Carbon nanotubes (CNTs) supported PtPd hollow nanospheres have been prepared by a replacement reaction between sacrificial cobalt nanoparticles and PtCl₆²⁻, Pd²⁺ ions. The morphology, elemental composition, structure and electrocatalytic properties of the PtPd hollow nanospheres have been investigated by transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction and typical electrochemical methods, respectively. The results indicate that the CNTs supported PtPd hollow nanospheres have excellent electrochemical properties for the electrooxidation of formic acid (high electrocatalytic activity and excellent stability) due to the high surface area resulted from the hollow nanosphere structure with porous shell.     

Exceptional size-dependent activity enhancement in the catalytic electroreduction of N2 over Mo nanoparticles

Electroreduction of N₂ to ammonia (NH₃) under ambient conditions, driven by renewable electricity, provides a promising alternative to the Haber-Bosch process and can reduce over 90% of CO₂ emissions via NH₃ synthesis. However, this process suffers from the shortage of efficient electrocatalysts. Herein, we report the size-dependent catalytic activity of Mo nanoparticles (NPs) in the size range of 1–10 nm for the electrochemical synthesis of NH₃ from N₂ and H₂O. Current density drastically increases as Mo size decreases. The mass activity of 1.5 nm Mo NPs reaches 27.6 μg h⁻¹ mg⁻¹_cat., which is higher than that of the best noble metal catalyst under comparable reaction conditions. Density functional theory (DFT) calculations show that the enhanced activity with a small size is due to an increase in edge sites between (110) and (100) surfaces. This condition weakens the binding of 1NH₂ and lowers the energy barrier of the second NH₃ desorption at the determining step.     

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

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

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

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

Hierarchical Co3O4 decorated PPy nanocasting core-shell nanospheres as a high performance electrocatalysts for methanol oxidation

In recent times, much attention has been paid to explore economic and highly active precious metal free electrocatalysts for energy conversion and storage systems due to the expensiveness of Pt-based catalysts. Here we developed a mesoporous core-shell like nanospheres composed of a metallic cobalt oxide core wrapped with a polypyrrole nanoshell (PPy/Co₃O₄) for methanol electrooxidation. The performance of the core-shell PPy/Co₃O₄ nanospheres as anodic catalyst material was measured in 1 M KOH electrolyte and the results obtained demonstrated that the hybrid possesses high catalytic activity in terms of current density and onset voltage. The core-shell PPy/Co₃O₄ delivers an oxidation current density of ～111 mA/cm² at 0.5 V with superior stability long run stability. The observed electrocatalytic performance of the porous PPy/Co₃O₄ nanospheres is attributed to the integrative effects of both Co-species and layered carbon shell and presence of exceptionally numerous mesopores. Results show evidence that the earth abundant PPy/Co₃O₄ provide a potential electrode material for methanol electrooxidation with a satisfactory reaction activity.