Monodisperse palladium–nickel alloy nanoparticles assembled on graphene oxide with the high catalytic activity and reusability in the dehydrogenation of dimethylamine–borane

Herein, a highly efficient and stable palladium nickel nanoparticles (PdNi NPs) supported on graphene oxide (GO) was synthesized, characterized and applied for the dehydrogenation of dimethyl ammonia borane (DMAB). The monodisperse PdNi NPs has been synthesized via the ultrasonic double solvent reduction method in the presence of oleylamine and GO as support matrices. The structure morphology and properties of PdNi@GO NPs were characterized by using different techniques such as UV–VIS, XPS, TEM, HRTEM and XRD methods. The PdNi@GO NPs was found to be highly effective and stable in the dehydrogenation of DMAB. This catalyst with the turnover frequency of 271.9 h^?1 shows one of the best results among the all prepared catalysts in literature for the dehydrogenation of DMAB. The apparent activation parameters of the catalytic dehydrogenation reaction were also calculated; apparent activation energy (E_a,app) = 38 ± 2 kJ mol^?1, activation enthalpy (ΔH^#_,app) = 35 ± 1 kJ mol^?1 and activation entropy (ΔS^#_,app) = ?102 ± 1 J K^?1 mol^?1.     

Highly efficient catalytic dehydrogenation of dimethyl ammonia borane via monodisperse palladium–nickel alloy nanoparticles assembled on PEDOT

Addressed herein, the synthesis of the monodisperse poly(3,4-ethylenedioxythiophene)(PEDOT) supported palladium–nickel nanomaterials (3.32 ± 0.36 nm) and their applications as a catalyst in dimethylamine-borane (DMAB) dehydrogenation is outlined. Microwave assistance procedure was used in preparation of nanomaterials where palladium and cobalt cations were reduced in PEDOT solution (Pd–Ni@PEDOT) in microwave conditions. The characterization of the nanocatalyst was performed by using UV-VIS, XRD, XPS, TEM and HR-TEM-EELS analyses. The Pd–Ni@PEDOT NPs were found to be highly effective and stable for the dehydrogenation of DMAB. The catalytic activity of Pd–Ni@PEDOT was one of the highest one among the all prepared catalysts in literature even at lower temperatures and concentrations, yielding to give high turnover frequency (451.2 h^?1) and low E_a (50.78 ± 2 kJ/mol) for dehydrocoupling of DMAB.     

Hierarchical reduced graphene oxide supported dealloyed platinum–copper nanoparticles for highly efficient methanol electrooxidation

Exploiting highly efficient electrocatalysts through simple methods is very critical to the development of energy conversion technologies. Herein, we develop a hierarchical reduced graphene oxide supported dealloyed platinum–copper nanoparticle catalyst (Pt–Cu/RGO) by a facile one-step electrodeposition of graphene oxide in the presence of H₂PtCl₆ and copper ethylenediamine tetraacetate. The nanostructure and composition were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Raman spectroscopy. Meanwhile, the electrocatalytic performance was investigated by cyclic voltammetry and chronoamperometry, showing that the Pt–Cu/RGO catalyst not only equips with an outstanding electrocatalytic activity for the methanol oxidation reaction (2.3 times that of commercial Pt/C catalyst), but also shows a robust durability and superior tolerance to CO poisoning. The excellent electrocatalytic performance could be attributed to the three-dimensional hierarchical structure, porous dealloyed nanoparticles and synergistic effect between each component.     

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.     

Fabrication of hollow metal oxide–nickel composite spheres and their catalytic activity for hydrolytic dehydrogenation of ammonia borane

In this paper, we report an effective approach to the fabrication of hollow titania–nickel composite spheres, hollow zirconia–nickel composite spheres, and hollow silica–nickel composite spheres. In this approach, metal oxide–nickel composite shells were coated on polystyrene particles by the sol–gel method and the polystyrene templates were dissolved subsequently, or even synchronously, in the same medium to form hollow spheres. Neither additional dissolution nor a calcination process was needed to remove the polystyrene templates. The as-prepared hollow metal oxide–nickel composite spheres were characterized by transmission electron microscopy. The catalytic activities of hollow titania–nickel composite spheres, hollow zirconia–nickel composite spheres, and hollow silica–nickel composite spheres for hydrolytic dehydrogenation of aqueous NaBH₄/NH₃BH₃ solution were compared. The evolutions of 64, 58, and 18 mL hydrogen were finished in about 49, 69, and 162 min in the presence of the hollow titania–nickel composite spheres, hollow zirconia–nickel composite spheres, and hollow silica–nickel composite spheres from aqueous NaBH₄/NH₃BH₃ solution, respectively. The molar ratios of the hydrolytically generated hydrogen to the initial NH₃BH₃ both in the presence of hollow titania–nickel composite spheres, hollow zirconia–nickel composite spheres, and hollow silica–nickel composite spheres are 2.8, 2.4, and 0.1 (the theoretical value of 3.0), respectively, indicating that the hollow titania–nickel composite spheres and hollow zirconia–nickel composite spheres show much higher hydrogen evolution rates and the amount of hydrogen evolution via hydrolytic dehydrogenation of ammonia borane than the hollow silica–nickel composite spheres. From the results of ATR-IR spectra, a certain amount of residual PS templates exists in hollow silica–nickel composite spheres, and the amount of the residual PS templates were able to be reduced by increasing the amount of aqueous ammonia solution used for the preparation. The catalytic activity of hollow silica–nickel composite spheres increases when the amount of residual PS templates decreases.     

TiO2–CdS supported CuNi nanoparticles as a highly efficient catalyst for hydrolysis of ammonia borane under visible-light irradiation

TiO₂–CdS nanotubes (NTs) were used for the first time as a support to load metal nanoparticles (NPs) for the hydrolysis of ammonia borane (AB) which is a new strategy. The TiO₂–CdS NTs support was first synthesized using a hydrothermal method, and then the CuNi NPs were loaded using a liquid-phase reduction method. The synthesized samples were characterized by XRD, SEM-EDS, TEM, XPS, ICP, UV–Vis, and PL analyses. The characterization results show that the CuNi NPs existed in the form of an alloy with a size of ~1.2 nm and uniformly dispersed on the support. Compared with their single metal counterparts, the bimetallic CuNi-supported catalysts showed a higher catalytic activity in the hydrolysis of AB under visible-light irradiation: Cu_0·45Ni_0·55/TiO₂–CdS catalyst had the fastest hydrogen evolution rate with a high conversion frequency (TOF) of 25.9 mol_H2·mol_cat⁻¹ min⁻¹ at 25 °C and low activation energy of 32.8 kJ mol⁻¹. Cu_0.45Ni_0.55/TiO₂–CdS catalyst showed good recycle performance, maintaining 99.3% and 85.6% of the original hydrogen evolution rate even after five and ten recycles, respectively. Strong absorption of visible light, improved electron–hole separation efficiency, and metal synergy between Cu and Ni elements played a crucial role in improving the catalytic hydrolysis performance of AB. The catalyst prepared in this study provides a new strategy for the application of photocatalysts.     

Preparation of Pt supported on mesoporous Mg–Al oxide catalysts for efficient dehydrogenation of methylcyclohexane

Hydrogen energy, characterizing by high-energy density, non-pollution and renewability, is regarded as an ideal clean green energy, and the chemical hydrogen storage is an optimal strategy to realize its large-scale utilization. In this study, to enhance the hydrogen evolution rate in the dehydrogenation of methylcyclohexane (MCH), Pt supported on Mg–Al oxide catalysts were prepared and the effects of the co-precipitation reaction time during the preparation of Mg–Al hydrotalcite on their structural properties were studied in detail. The results showed that both the pore diameter and Pt dispersion were increased after prolonging the precipitation reaction time. During the dehydrogenation of MCH, these resultant catalysts presented high activity and good stability: hydrogen evolution rate reached up to 1892 mmol·g_Pt^?1 min^?1 at 623 K and the conversion was still held at 92% after 218 h. Of course, a slight decrease on the conversion during the dehydrogenation reaction was also observed, which was mainly attributed to the aggregation of Pt particles at high temperature.     

Surfactant-free Pd–Fe nanoparticles supported on reduced graphene oxide as nanocatalyst for formic acid oxidation

Herein, a novel surfactant-free nanocatalyst of Pd–Fe bimetallic nanoparticles (NPs) supported on the reduced graphene oxide (Pd–Fe/RGO) were synthesized using a two-step reduction in aqueous phase. Electrochemical studies demonstrate that the nanocatalyst exhibits superior catalytic activity towards the formic acid oxidation with high stability due to the synergic effect of Pd–Fe and RGO. The optimized Pd–Fe/RGO (Pd:Fe = 1:5) nanocatalyst possess an specific activity of 2.72 mA cm^?2 and an mass activity of 1.0 A mg^?1_(Pd), which are significantly higher than those of Pd/RGO and commercial Pd/C catalysts.     

One-step synthesis of Cu@FeNi core–shell nanoparticles: Highly active catalyst for hydrolytic dehydrogenation of ammonia borane

This paper investigates a facile and one-step synthesis of trimetallic magnetic Cu@FeNi core–shell nanoparticles, which are composed of crystalline Cu cores and amorphous FeNi shells, at room temperature under ambient atmosphere within 2 min. It is found that among the Cu@FeNi system, Cu_0.4@Fe_0.1Ni_0.5 shows the best synergistic performance for catalyzing the hydrolytic dehydrogenation of ammonia borane with the activation energy of 32.9 kJ/mol, being lower than most of the reported data, and the catalytic activity of Cu_0.4@Fe_0.1Ni_0.5 is much better than its monometallic, bimetallic and trimetallic counterparts whether in states of pure metals, alloys or physical mixtures. Further, the present catalyst has a good recycle stability with an easy magnetic separation method.     

Platinum–Iron nanoparticles supported on reduced graphene oxide as an improved catalyst for methanol electro oxidation

Platinum–Iron nanoparticles supported on reduced graphene oxide powder are synthesized by chemical reduction method as an anode catalyst for the methanol electro oxidation. The characterization of the catalyst has been investigated using physical and electrochemical methods. Prepared catalyst was characterized by scanning electron microscopy (SEM), TEM (Transmission electron microscopy), FT-IR (Fourier-transform infrared spectroscopy), Raman spectroscopy and, X-ray diffraction (XRD) and energy dispersive analysis of X-ray (EDX). Pt and Pt-Fe nanoparticles are uniformly dispersed on the surface of reduced graphene oxide (rGO) powder nanocomposite support. The catalytic properties of the catalyst for methanol electro-oxidation were thoroughly studied by electrochemical methods that involved in the cyclic voltammetry, linear sweep voltammetry (LSV), chronoamperometry and electrochemical impedance spectroscopy (EIS). The Pt-Fe/rGo exhibits high electrocatalytic activity, catalyst tolerance for the CO poisoning and catalyst durability for electro-oxidation of methanol compared to the Pt/rGo and commercial Pt/C catalyst. Therefore, the Pt-Fe/rGo catalyst is a good choice for application in direct methanol fuel cells.     

Bimetallic palladium–iridium alloy nanoparticles as highly efficient and stable catalyst for the hydrogen evolution reaction

Addressed herein, a highly efficient, durable and uniformly dispersed activated carbon supported palladium–iridium nanomaterials (3.42 ± 0.34 nm) were reported for the first time as a catalyst in dimethylamine-borane dehydrogenation reaction at the room temperature. The activated carbon supported palladium-iridium nanosheet (Pd–Ir NPs) is obtained by a simple ultrasonic reduction method, and the fabricated nanocatalyst have been defined by Ultra-Violet-Visible (UV–VIS), Raman spectroscopy, X-Ray Diffraction (XRD), X-Ray Photoelectron Spectroscopy (XPS), Transmission Electron Microscopy (TEM) and High-Resolution Transmission Electron Microscopy (HR-TEM). These newly prepared Pd–Ir nanocomposites were found to be highly efficient and stable for dehydrocoupling of dimethylamine borane. The catalytic activity of the Pd–Ir NPs was excellent by showing the one of the best catalytic activity with a very high turnover frequency (295.1 h^?1) and low E_a value of 36.6 ± 2 kJ/mol for DMAB dehydrocoupling. Another important fact about the prepared catalyst is the reusability of the catalyst was very high and easily reused five times without any significant decrease in their catalytic performance. In the current work, the synthesize, characterization and the catalytic performance of the Pd–Ir nanoparticles for the dehydrogenation of the DMAB reaction will be discussed in detail.     

Polymer-graphene hybride decorated Pt nanoparticles as highly efficient and reusable catalyst for the dehydrogenation of dimethylamine–borane at room temperature

Addressed herein, we report a reduced graphene oxide (rGO) nanosheet coupled with polyaniline (PANI) for platinum (Pt) nanoparticles as supporting materials. The PANI-coupled rGO (PANI@rGO) nanosheet is prepared by a simple one-step chemical assembly strategy, and Pt nanoparticles are anchored on the support of PANI@rGO through the reaction of PANI with a platinum salt. The designed PANI efficiently exposes the surface of rGO sheets and stabilizes metal nanoparticles. Consequently, the Pt@PANI-rGO catalyst exhibits good reusability, durability and high catalytic performance for dimethylamine–borane dehydrogenation reaction. The structure morphology and properties of Pt@PANI-rGO NPs were characterized by using several different techniques such as UV–Vis, XPS, TEM, XRD and HR-TEM-EDX analyses. This newly prepared catalyst can be reused again at low concentrations and temperature. They showed a high turnover frequency (42.94 h^?1) and low E_a value of 15.1 ± 2 kJ/mol for DMAB dehydrocoupling in the ambient conditions. The proposed nano architecture offers a new pathway to promote the performances of rGO in various applications; moreover, this work provides a powerful and universal synthetic strategy for such an architecture.     

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.     

Fabrication of hollow silica–alumina composite spheres and their activity for hydrolytic dehydrogenation of ammonia borane

In this study, we investigated the influence of the preparation conditions of hollow silica–alumina composite spheres on their activity for the hydrolytic dehydrogenation of ammonia borane. Hollow silica–alumina composite spheres were prepared by polystyrene template method, and the polystyrene template particles were removed by calcination. The as-prepared hollow spheres were calcined at 523–873 K for 3 h. From the results of elemental analysis, polystyrene templates were completely removed by calcination at 873 K. small particles around the hollow spheres were observed from the images of transmission electron microscopy. To obtain homogeneous hollow spheres, the as-prepared hollow spheres were calcined at 873 K for 0–12 h. From the results of transmission electron microscopy, homogeneous hollow spheres were obtained by calcination for 0 h. The activity of the hollow spheres was the 2.6 times higher that of the hollow spheres calcined for 3 h. From the results of activity tests and ammonia temperature-programming desorption, the activity of the hollow spheres depends on amount of acid sites.     

PVP-stabilized Co–Ni nanoparticles as magnetically recyclable catalysts for hydrogen production from methanolysis of ammonia borane

Hydrogen production by hydrolysis of ammonia borane has been studied extensively, but the methanolysis has been progressing slowly, especially with non-noble metals as low cost catalyst, which is limited by complicated preparation methods or not conducive to actual application. Herein, a series of magnetically recyclable bimetallic Co–Ni nanoparticles were produced by a facile solution-phase reduction technique, using polyvinylpyrrolidone (PVP) as the stabilizing agent. The as-prepared Co–Ni alloys were amorphous and highly dispersed. Among six different PVP-stabilized Co_1-xNi_x nanoparticles (x = 0, 0.1, 0.3, 0.5, 0.7, 1) studied, the PVP-stabilized Co_0.7Ni_0.3 nanoparticles show the best catalytic performance with a TOF value of 35.3 mol_H2/(mol_catalyst·min) for hydrogen production from methanolysis of ammonia borane at 298 K, showing good synergistic effect between Co and Ni. Moreover, the catalyst can remain 91.2% initial catalytic activity after eight cycles, showing excellent stability and magnetic recyclability.     

Three-dimensional reduced graphene oxide–Mn3O4 nanosheet hybrid decorated with palladium nanoparticles for highly efficient hydrogen evolution

A three-dimensional (3D) reduced graphene oxide–Mn₃O₄ nanosheet (Mn₃O₄@rGO) hybrid was achieved by simple electrodeposition technique. Small palladium nanoparticle were homogeneously anchored onto Mn₃O₄@rGO substrate through the reduction of palladium salt. The interpenetrating network architecture of Mn₃O₄@rGO greatly inhibited the aggregation of 2D sheets of Mn₃O₄ and rGO, and the open 3D orientation of the Mn₃O₄@rGO hybrid nanosheets on the electrode facilitated both mass transport and electron transfer as well as maximally exposed active sites. The introduction of Mn₃O₄ enhanced the structural and electrochemical stability of rGO. The as-synthesized Pd/Mn₃O₄@rGO hybrid was employed as an electrocatalyst for electrocatalytic hydrogen evolution reaction (HER). The electrocatalyst showed a low overpotential of 20 mV at 10 mA cm^?2, a small Tafel slope of 48.2 mV dec^?1, and a large exchange current density of 0.59 mA cm^?2. Importantly, the catalyst possessed superior durability with 85.87% of catalytic activity after a long-time test (10 h). This work presents a simple and efficient stratagy to construct high-performance electrocatalysts for energy and environmental applications.     

Facile one-step fabrication of bimetallic Co–Ni–P hollow nanospheres anchored on reduced graphene oxide as highly efficient electrocatalyst for hydrogen evolution reaction

It is significant but challenging to develop noble-metal-free electrocatalysts exhibiting high activity and long-term stability toward hydrogen evolution reaction (HER) to satisfy the ever-increasing demand for clean and renewable energy. Herein, an environment-friendly and low-temperature electroless deposition method is developed for the synthesis of Co–Ni–P hollow nanospheres anchored on reduced graphene oxide nanosheets (Co–Ni–P/RGO). By optimizing the molar ratio of Ni/Co precursor, composition dependent electrocatalytic performances toward HER of nanostructured Co–Ni–P/RGO electrocatalyst are investigated in 1.0 M KOH solution. The results suggest that when the molar ratio of Ni/Co precursor is 3/7, as-prepared ternary Co–Ni–P/RGO electrocatalyst exhibits a remarkably enhanced HER activity in comparison to binary Ni–P/RGO and Co–P/RGO electrocatalysts, delivering a current density of 10 mA cm⁻² at the overpotential of only 207 mV. The value of Tafel slope for nanostructured Co–Ni–P/RGO electrocatalyst reveals that HER process undergoes Volmer-Heyrovsky mechanism. Besides, nanostructured Co–Ni–P/RGO electrocatalyst features superior stability under alkaline condition. The results suggest that nanostructured composite of Co–Ni–P hollow nanospheres/RGO is a potential candidate for hydrogen production through water splitting.