RESUMEN
In recent years, preparing precious metal catalysts with a controllable morphology has become a hot research topic for researchers. In this study, monodispersed palladium (Pd) nanoparticles (NP) and ultrathin Pd twisty nanowire networks (TNN) were synthesized in a solvothermal system using N,N-dimethylformamide (DMF) and oleylamine (OAm) as solvents, Transmission electron microscopy (TEM) images reveal the successful synthesis of nanoparticles and ultrathin TNN microstructures. Electrochemical data show that the current densities of Pd-NP and Pd-TNN for the ethanol oxidation reaction (EOR) reach 1878 mA mg-1 and 1765 mA mg-1, respectively. Compared to commercial Pd/C, Pd-TNN and Pd-NP exhibit better catalytic stability, lower electron transfer barriers, and more resistance to catalyst poisoning. Temperature, pH value, and ethanol concentration are all favorable for the EOR. According to the experimental data, the mechanism of enhanced electrocatalytic activity of Pd-NP and Pd-TNN catalysts for ethanol oxidation is discussed. This paper presents a method for preparing catalysts with stabilized structures to develop Pd-based catalysts for electrocatalytic oxidation reactions.
RESUMEN
High-entropy alloy nanoparticles (HEA NPs) have aroused great interest globally with their unique electrochemical, catalytic, and mechanical properties, as well as diverse activity and multielement tunability for multi-step reactions. Herein, a facile low-temperature synthesis method at atmospheric pressure is employed to synthesize Pd-enriched-HEA-core and Pt-enriched-HEA-shell NPs with a single phase of face-centred cubic structure. Interestingly, the lattice of both Pd-enriched-HEA-core and Pt-enriched-HEA-shell enlarge during the formation process of HEA, with tensile strains included in the core and shell of HEA. The as-obtained PdAgSn/PtBi HEA NPs show excellent electrocatalytic activity and durability for methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR). The specific (mass) activity of PdAgSn/PtBi HEA NPs for MOR is 4.7â mA cm-2 (2874â mA mg(Pd+Pt) -1 ), about 1.7 (5.9) and 1.5 (4.8) times higher than that of commercial Pd/C and Pt/C catalysts, respectively. Additional to high-entropy effect, Pt sites and Pd sites on the interface of the HEA act synergistically to facilitate the multi-step process towards EOR. This study offers a promising way to find a feasible route for scalable HEA manufacturing with promising applications.
RESUMEN
In recent times, the fabrication of noble metal-based catalysts with controllable morphologies has become a research hotspot. Electrocatalytic devices with excellent catalytic performance and enhanced durability for the ethylene glycol oxidation reaction (EGOR) and the glycerol oxidation reaction (GOR) are significant for commercial direct fuel cells. Herein, a series of PdPb sea urchin-like nanodendrite (ND) structures with controllable molar ratios were synthesized as EGOR and GOR electrocatalysts of high efficiency. The optimized structurally regular Pd3Pb NDs exhibit the best electrocatalytic activity and outstanding stability compared to other samples and commercial Pt/C. In addition, the integrated Pb on Pd3Pb NDs can mitigate the bond energy the intermediates generate and further boost the electrooxidation of the intermediates by supplying enough active sites without considering its intrinsic structure, which is beneficial to the enhanced EGOR and GOR activity and stability. With the assistance of electrochemical measurement, the mechanism of the enhanced alloy was further investigated. This paper presents a promising strategy to fabricate catalysts with stable structures, which will elucidate a very promising approach for developing Pd-based catalysts for further applications in fuel cells.
RESUMEN
Synthesizing alloyed bimetallic electrocatalysts with a three-dimensional (3D) structure assembly have arouse great interests in electrocatalysis. We synthesized a class of alloyed Pd3Pb/Pd nanosheet assemblies (NSAs) composed of a two-dimensional (2D) sheet structure with adjustable compositions via an oil bath approach at a low temperature. Both the scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images reveal the successful formation of the nanosheet structure, where the morphology of Pd3Pb/Pd NSAs can be regulated by adjusting the atomic mole ratio of Pb and Pb metal precursors. The power X-ray diffraction (XRD) pattern shows that Pd3Pb/Pd NSA catalysts are homogeneously alloyed. Electrochemical analysis and the density functional theory (DFT) method demonstrate that the electrocatalytic activity of the alloyed Pd3Pb/Pd NSAs can be improved by the doping of the Pb element. As a result of the addition of element Pb and change of the electron structure, the electrocatalytic activity toward ethanol oxidation of alloyed Pd3Pb/Pd-15 NSA can reach up to 2886 mA mg-1, which is approximately 2.8 times that of the pure Pd NSA counterpart (1020 mA mg-1). The Pd3Pb/Pd NSAs are favorable in a high catalytic temperature, high KOH concentration, and high ethanol concentration.
RESUMEN
The direct ethanol fuel cells in an alkaline medium have a broad vision of applications because of their large energy density, reasonable power density, and environmentally friendly features. Herein, we present a facile one-step method to synthesize PdAg nanosheet assemblies (NSAs) in a mixed solution of N,N-dimethylformamide and water with the addition of molybdenum hexacarbonyl and cetyltrimethylammonium bromide. Pure Pd NSA shows an irregular shape while PdAg NSAs gradually undergo a process from solid assembly to a hollow structure with the Pd/Ag molar ratio changing from 3:1 to 2:1 to 1:1. The formation of alloy nanosheets in the assemblies combined with the introduction of Ag in the Pd catalyst enhances the catalytic activity toward ethanol electrooxidation from 1524 mA mg-1 of pure Pd NSA to 1866 mA mg-1 of PdAg NSA with a Pd/Ag molar ratio of 2:1. On the basis of the experimental data, compared with pure Pd structures, both the nature of a thin nanosheet of PdAg NSAs and the structural changes in the alloy assemblies play key roles in determining the electrocatalytic activity of these Pd-based catalysts.