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.     

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.     

One-pot sonication-assisted polyol synthesis of trimetallic core–shell (Pd,Co)@Pt nanoparticles for enhanced electrocatalysis

In this report, the synthesis and characterization of trimetallic (Pd,Co)@Pt nanoparticles (NPs) with Pt-enriched surfaces are detailed. (Pd,Co)@Pt NPs supported on carbon with different elemental compositions (Pd₅₀Co₂₀Pt₃₀, Pd₃₄Co₂₇Pt_39, and Pd₂₁Co₃₄Pt₄₅) are synthesized by sonochemical reactions of Pt(acac)₂, Pd(acac)₂, and Co(acac)₂ in ethylene glycol. The NPs are subsequently characterized by X-ray diffractometry, transmission electron microscopy, and inductively coupled plasma − atomic emission spectroscopy to determine their particle size, morphology, and elemental composition. The existence of a Pt-enriched surface on the (Pd,Co)@Pt NPs is demonstrated by line profiles obtained via scanning transmission microscopy − energy dispersive spectroscopy. The NPs are applied to electrocatalysis for oxygen reduction reactions. When compared to a commercial Pt catalyst, the onset potential of the NPs increased by 22 mV, while the specific and mass activities were enhanced by factors of ∼ 2.7–4.9 and 4.3–6.3, respectively. The (Pd,Co)@Pt NPs also showed superior stability, as the onset potential was reduced by 11–19 mV after 5000 potential cycles when compared to the 45 mV reduction observed for a commercial Pt catalyst.     

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.     

Hydride destabilization in core–shell nanoparticles

We present a model that describes the effect of elastic constraint on the thermodynamics of hydrogen absorption and desorption in biphasic core–shell nanoparticles, where the core is a hydride forming metal. In particular, the change of the hydride formation enthalpy and of the equilibrium pressure for the metal/hydride transformation are described as a function of nanoparticles radius, shell thickness, and elastic properties of both core and shell. To test the model, the hydrogen sorption isotherms of Mg–MgO core–shell nanoparticles, synthesized by inert gas condensation, were measured by means of optical hydrogenography. The model's predictions are in good agreement with the experimentally determined plateau pressure of hydrogen absorption. The features that a core–shell systems should exhibit in view of practical hydrogen storage applications are discussed with reference to the model and the experimental results.     

Preparation and characterization of core–shell-like PbPt nanoparticles electro-catalyst supported on graphene for methanol oxidation

PbPt core–shell-like nanoparticles supported on graphene is successfully synthesized by a simply galvanic displacement reaction method. The composition, morphology, structure of the catalyst and activity towards methanol oxidation are characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV). Chronoamperometric and CV results reveal that PbPt core–shell-like nanoparticles catalyst has better activity towards methanol oxidation than the pure platinum prepared under the same conditions. These behaviors are attributed to an electronic effect of the inner Pb or the increase in the d-orbital vacancy of Pt in core–shell-like PbPt catalyst.     

Synthesis and electrocatalytic performance of MWCNT-supported Ag@Pt core–shell nanoparticles for ORR

Ag@Pt core–shell nanoparticles with different Ag/Pt ratios were supported on multi walled carbon nanotubes (MWCNTs) and used as electrocatalysts for PEMFC. The morphology of the electrocatalyst samples was characterized by XRD and HRTEM. It was found that the Ag@Pt/MWCNTs catalyst exhibited a core–shell nanostructure. And the CV and LSV results demonstrated that such core–shell materials exhibited attractive electrocatalytic activity. Moreover, the specific electrochemically active area (EAS) of the Ag@Pt/MWCNTs catalyst is 70.63 m² g⁻¹, which is higher than the values reported in the literature.     

Ru@Pt core–shell nanoparticles for methanol fuel cell catalyst: Control and effects of shell composition

The present work presents a method to encapsulate pre-synthesised Ru nanoparticles (NPs) by Pt using a polyol method without capping agents at various pH values (6, 7, 8 and 10). The structural and surface properties of the catalysts were characterised using X-ray diffraction, transmission electron microscopy, CO stripping, and energy-dispersive X-ray spectroscopy. The studies suggest that the pH during encapsulation of Ru by Pt plays an important role in controlling of shell composition. A core–shell catalyst with an alloy shell was obtained at a pH of 6, whereas a monometallic Pt shell was obtained at a pH of 10. The core–shell catalysts gave higher steady-state current for methanol oxidation: 10-fold higher for alloy shells and 5-fold higher for Pt-enriched shells compared to the pure Pt catalyst. It is suggested that the highest catalytic enhancement of the core–shell catalysts is obtained through the bi-functional character that dominates the alloy shells rather than the ligand-effect-promoted Pt-enriched shells.     

Synthesis and electrocatalytic alcohol oxidation performance of Pd–Co bimetallic nanoparticles supported on graphene

Magnetic Pd–Co bimetallic nanoparticles supported on reduced graphene oxide sheets (Pd–Co/RGO) with excellent electrocatalytic performance have been synthesized by a rapid reducing method, using sodium hypophosphite as the reducing agent. The loading and crystalline phase of cobalt in the Pd–Co/RGO hybrids varied as to the initial amount of cobalt salt and reducing agent. Transmission electron microscopy images show that the mean size of the Pd–Co bimetallic nanoparticles was about 10–13 nm and without significant agglomeration. At the same Pd loading on graphene, the current densities of the forward anodic peak of the different Pd–Co/RGO catalysts was decreased by about 25% when compared with that of the pure Pd nanoparticles supported on reduced graphene oxide for both methanol and ethanol oxidation. However, chronoamperometry tests confirmed that the stability was increased by up to 240% and 225% for methanol oxidation and ethanol oxidation, respectively. It is hypothesized that the Co layer on Pd partially blocks Pd sites sacrificing a small portion of the activity of the catalysts, but it leaves the remaining Pd more active and thus enhances alcohol oxidation kinetics and tolerance to poisoning intermediates. Catalytic performance of the Pd–Co/RGO hybrids for alcohol oxidation is primarily affected by the interaction among Pd, Co, and graphene.     

A strategy for easy synthesis of carbon supported Co@Pt core–shell configuration as highly active catalyst for oxygen reduction reaction

An oxygen-mediated galvanic battery reaction strategy has been developed to one-step synthesize carbon-supported Co@Pt core–shell nanostructures. Relying on this strategy, a structural evolution of 3-D Pt-on-Co bimetallic nanodendrites into Co@Pt core–shell configuration is readily achieved in our study. These well-supported and low-Pt-content nanostructures show superior electrocatalytic activities to oxygen reduction reaction. Especially, the supported Co@Pt core–shell electrocatalyst for oxygen reduction reaction shows a high activity with the maximal Pt-mass activity of 465 mA mg⁻¹ Pt at 0.9 V (vs. RHE). The present investigation clearly demonstrates that the design and synthesis of the core–shell nanostructures is a viable route for building Pt-based electrocatalysts with optimized utilization efficiency and higher cost performance.     

Synthesis and characterization of Cu core Pt–Ru shell nanoparticles for the electro-oxidation of alcohols

Cu@Pt–Ru core–shell supported electrocatalysts have been synthesized by a two-step process via a galvanic displacement reaction. XRD diffraction and EDX analysis, and cyclic voltammetry measurements revealed the presence of nanoparticles composed by a Cu-rich Pt–Cu core surrounded by a Pt-rich Pt–Ru shell. Cyclic voltammetry and chronoamperometric measurements showed that as-synthesized core–shell materials exhibit superior catalytic activity towards methanol and ethanol electro-oxidation compared to a commercial Pt–Ru/C catalyst with higher Pt loading. This behavior can be associated with the lattice mismatch between the Pt-rich shell and the Cu rich core, which in turn produces lattice-strain, surface ligand effects and a large amount of surface defect sites. In addition, the core–shell electrodes displayed a better catalytic activity and lower onset potentials for ethanol oxidation than for methanol oxidation.     

Amino functionalized carbon nanotubes supported CoNi@CoO–NiO core/shell nanoparticles as highly efficient bifunctional catalyst for rechargeable Zn-air batteries

Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are the core reaction processes of rechargeable Zn-air battery (ZAB) cathode. Therefore, exploring a bifunctional catalyst with excellent electrochemical performance, high durability, and low cost is essential for rechargeable ZAB. In this work, amino functionalized carbon nanotubes supported core/shell nanoparticles composed of CoNi alloy core and CoO–NiO shell (CoNi@CoO–NiO/NH₂-CNTs-1) is synthesized through a simple and efficient hydrothermal reaction and calcination method, which shows higher ORR/OER bifunctional catalytic performance than the single metal-based catalyst, such as Ni@NiO/NH₂-CNTs and Co@CoO/NH₂-CNTs. The fabricated bimetallic alloy based catalyst CoNi@CoO–NiO/NH₂-CNTs-3 with the optimized loading content of CoNi@CoO–NiO core/shell nanoparticles, presents the best bifunctional catalytic performance for ORR/OER. Experimental studies reveal that CoNi@CoO–NiO/NH₂-CNTs-3 exhibits the onset potential of 0.956 V and 1.423 V vs. RHE for ORR and OER, respectively. It also exhibits a low overpotential of 377 mV to achieve a 10 mA cm^?2 current density for OER, and positive half-wave potentials of 0.794 V for ORR. And the potential difference between half-wave potential of ORR (E_1/2) and the potential at 10 mA cm^?2 for OER (E_j10) is 0.813 V. In addition, when CoNi@CoO–NiO/NH₂-CNTs-3 is used as an air electrode catalyst of rechargeable ZAB, its maximum power density and open circuit voltage (OCV) can reach 128.7 mW cm^?2 and 1.458 V (The commercially available catalyst of Pt/C–RuO₂ is 88.1 mW cm^?2), which strongly demonstrates that the fabricated catalyst CoNi@CoO–NiO/NH₂-CNTs-3 can be used as a highly efficient bifunctional catalyst for ZABs, and is expected to replace those expensive precious metal electrocatalysts to meet the growing demand for new energy devices.     

Electro-oxidation of formate-based solutions on Au/Pd core–shell nanoparticles – Experiment and simulation

Au/Pd core–shell nanoparticles (NPs) were employed to study electro-oxidation mechanism of formate-based solutions. A series of combined studies including Raman spectroscopy, electrochemical stripping analysis, and computational simulations were conducted to understand electro-oxidation of formate-based solutions on the Au/Pd NPs. Compared to the commercial Pd black, the Au/Pd NPs showed superior catalytic activities, especially when using concentrated formate solutions. CO stripping test in conjunction with in situ Raman studies showed a lower oxidation potential (0.6 V vs. Ag/AgCl) of CO on the Au/Pd NPs than the Pd black (>0.6 V). This indicated a strong electronic coupling between Au and Pd in the core–shell NPs which could enhance the oxidation of formate species. In addition, theoretical studies suggested lower formate and hydroxyl coverages at the same applied potential for the Au/Pd NPs than the Pd black in the formate-based solutions, shedding lights on their superior formate-oxidizing ability.     

Novel core–shell structure of perovskite anode and characterization

The core–shell anode particulates are prepared with perovskite core of (Sr_0.7La_0.3)(Ti_1−xNb_x)O₃ and the shell of multiple elements doped solid electrolyte (La_0.75Sr_0.2Ba_0.05)_0.175Ce_0.825O_1.891 (LSBC) by a citric acid-based combustion (SV) coating process. The ionic shell LSBC precedes the peak reduction–oxidation reaction temperature of the anode to 500 °C. The selected coverage ratio of 1.5 or 3.0 mol% LSBC shell on the core is used to ensure appropriate electrocatalytic activity and electronic conductivity. The core–shell anode increases the interface charge transfer (ReZ(i)) and chemical catalysis (ReZ(c)) that is revealed on the reduction of AC impedance. The lower slope of the voltage drop for the half-cell, which is composed of the core–shell anode, indicates the increasing effective triple phase boundary (TPB) sites and reduces the interface thermal expansion and lattice matching, as well as extends the ionic conduction path from LSBC electrolyte to the core–shell anode. The power density increases three times by using the core–shell structural anode than without using the core–shell anode in the half-cell.     

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.     

Electrochemical performance of Pd and Au–Pd core–shell nanoparticles on surface tailored carbon black as catalyst support

The present work studies the influence of the surface chemistry of carbon supports on the electrochemical behaviour of Pd and Au–Pd core–shell (CS) nanoparticles. Vulcan XC-72R was chemically modified by different acid treatments, inducing changes in the volume of the mesopores and surface density of oxygenated species. The CS nanostructures featuring 19 nm Au cores and 10 nm Pd shells were synthesized by colloidal methods and subsequently incorporated to the carbons supports. Pd nanoparticles were prepared by impregnating a Pd precursor into the modified carbons followed by reduction with sodium borohydride. The use of different preparation methods allowed the independent study of the effect of the support on the morphology/distribution of the nanoparticles and on the reactivity of the nanoparticles, through their interaction with organic molecules. The electrocatalysts were characterised by XRD, EDX, Raman spectroscopy and contact angle measurements. CO and formic acid (HCOOH) electro-oxidation were studied using cyclic voltammetry and chronoamperometry. The effect of the carbon support on the electrocatalytic activity was highly dependent on the method of preparation. Pd nanoparticles obtained by impregnation showed higher HCOOH oxidation currents when supported on the highly oxidised Vulcan support. This is due to the generation of smaller particle sizes (2.3 nm) as a result of the high density of oxygenated functional groups. On the other hand, the CS nanostructures are significantly less active in highly oxidised Vulcan as a results of specific chemical interactions which may be related to the formation of oxides. The implication of these findings towards rationalising particle–substrate interactions are briefly discussed.     

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.     

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.     

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.     

A straightforward one-pot synthesis of Pd–Ag supported on activated carbon as a robust catalyst toward ethanol electrooxidation

Direct Ethanol Fuel Cells (DEFCs) have fascinated remarkable attention on account of their high current density and being environmentally friendly. Developing efficient and durable catalysts with a simple and fast method is a great challenge in the practical applications of DEFCs. To this end, the bimetallic Pd–Ag with adjustable Pd:Ag ratios were synthesized via a simple and one-pot strategy on activated carbon as a support in this study. The Pd–Ag/C catalysts with different molar ratios were synthesized by simultaneous reduction of Pd and Ag ions in the presence of the ethanolic sodium hydroxide as a green reducing agent for the first time. Several different methods, including FE-SEM, HR-TEM, XRD, XPS EDX, ICP-OES, and BET were used to confirm the structure and morphology of the catalysts. The performance of catalysts was also examined in ethanol oxidation. Obtained results of electrochemical experiments revealed that the Pd₃–Ag₁/C catalyst had superior catalytic activity (2911.98 mAmg^?1_Pd), durability, and long-stability compared to the other catalysts. The excellent catalytic characteristic can be attributed to the synergistic effect between Pd and Ag. We presume that our simple method have the chance to be utilized as a proper method for the synthesis of fuel cell catalysts.