Electrocatalytic Surface Area Research Articles

Preparation of high active Pt/C cathode electrocatalyst for direct methanol fuel cell by citrate-stabilized method

Platinum nanoparticles supported on carbons (Pt/C, 60%, mass fraction) electrocatalysts for direct methanol fuel cell (DMFC) were prepared by citrate-stabilized method with different reductants and carbon supports. The catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and cyclic voltammetry (CV). It is found that the size of Pt nanoparticles on carbon is controllable by citrate addition and reductant optimization, and the form of carbon support has a great influence on electrocatalytic activity of catalysts. The citrate-stabilized Pt nanoparticles supported on BP2000 carbon, which was reduced by formaldehyde, exhibit the best performance with about 2 nm in diameter and 66.46 m 2/g (Pt) in electrocatalytic active surface (EAS) area. Test on single DMFC with 60% (mass fraction) Pt/BP2000 as cathode electrocatalyst showed maximum power density at 78.8 mW/cm 2.

Synthesis of Pt Nanopetals on Highly Ordered Silicon Nanocones for Enhanced Methanol Electrooxidation Activity

Platinum (Pt) nanopetals were electrodeposited on highly ordered silicon nanocones (SiNCs) and explored as the electrocatalyst for methanol oxidation reaction (MOR) for direct methanol fuel cells applications. Highly ordered SiNCs array fabricated using the porous anodic aluminum oxide as the template had a high surface area. Well-dispersed Pt nanopetals possessing high electrocatalytic surface area was synthesized by pulse-electrodeposition on the SiNCs. Pt nanopetals loaded on highly ordered SiNC support exhibited very good catalytic activity for MOR and a high tolerance against CO poisoning, as compared to Pt nanoflowers/flat Si, Pt nanoparticles/flat Si, and many previously reported works. The abundance of a large surface area for facile transport of methanol, SiO(2) sites in the vicinity of the SiNCs, as well as less contact area between the Pt nanopetals catalyst and SiNCs are suggested to be the major factors enhancing the electrocatalytic performance of the Pt nanopetal/SiNC electrode. Moreover, we believe this new nanostructure (Pt nanopetals/SiNCs) will enable many new advances in nanotechnology.

Electrocatalytic activity of Pt nanoparticles electrodeposited on amorphous carbon-coated silicon nanocones

This study pulse-electrodeposits Pt nanoparticles on amorphous carbon-coated silicon nanocones (ACNCs) and explores them as the electrocatalyst for methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) for direct methanol fuel cell applications. The work prepares silicon nanocones on the Si wafer using porous anodic aluminum oxide as the template and then deposits the amorphous carbon layer on the nanocones by microwave plasma chemical vapor deposition. According to Raman scattering and X-ray photoelectron spectroscopies (XPS), the surface of the ACNC support is composed of a nanocrystalline graphitic structure, and rich in oxygen-containing adspecies. The Pt nanoparticles pulse-electrodeposited on the highly ordered ACNC support disperses well with a large electrocatalytic surface area. The Pt/ACNC electrode exhibits excellent electrocatalytic activity and stability toward both MOR and ORR. This study suggests the abundant oxygen-containing surface species and the nanometer size of the Pt catalyst as the two major factors enhancing electrocatalytic performance of Pt/ACNC electrode. The XPS study suggests the occurrence of charge transfer from π-sites of the graphitic structure to the Pt nanoparticle, thereby improving the electrochemical stability of the electrode.

Magnetically moveable bimetallic (nickel/silver) nanoparticle/carbon nanotube composites for methanol oxidation

Multi-walled carbon nanotubes (CNTs) functionalized both by nickel and silver nanoparticles were obtained using a single step chemical deposition method in an ultrasonic bath. The new composite material was characterized by means of scanning electron microscopy (SEM), X-ray diffraction (XRD) and cyclic voltammetry (CV). The electroactivity of the bi-functionalized CNTs multi-walled carbon nanotubes was assessed in respect to the electrooxidation of methanol. It was found that the carbon nanotube supported silver nanoparticles have significantly higher catalytic properties than the bulk metal of the same surface area. Furthermore, it was shown that the presence of only a very small proportion of magnetic nickel nanoparticles (1.5% of the total number of metallic nanoparticles) allows the bi-functionalized carbon nanotubes to be moved magnetically in solution, making them easily recoverable after use whilst keeping an optimal electrocatalytic surface area.

Electrochemical properties of ball-milled LaMg12–Ni composites containing carbon nanotubes

Abstract Nanocrystalline LaMg 12 –Ni composites containing carbon nanotubes (CNTs) were prepared by two ball-milling ways, and the resulting microstructure and electrochemical characteristics were investigated. It is found that the discharge capacities and high-rate dischargeabilities (HRDs) of the CNT-containing composites prepared by ball-milling as-prepared nanocrystalline LaMg 12 –Ni composite and CNTs for 1 h (denoted as Composite-CNT1-1) were obviously higher than that by ball-milling LaMg 12 alloy, Ni powder and CNT1 together for 12 h (denoted as Composite-CNT1-2). The highest discharge capacity reaches 999.8 mA h/g. Raman spectra and X-ray diffraction (XRD) patterns show that the structure of the CNTs still exists and the defect increases in Composite-CNT1-1. However, in Composite-CNT1-2, due to the overlong ball-milling time, the crystalline structure of the CNTs has been destroyed and amorphous carbons have formed. Cyclic voltammetry and electrochemical impedance spectra measurements indicate that the CNT modification in Composite-CNT1-1 increases the electrocatalytic activity and surface area, which leads to its higher discharge capacity and HRD. The larger electrochemical reaction resistance caused by amorphous carbon in Composite-CNT1-2 results in its lower discharge capacity and HRD. The CNT modification has negligible effect on the diffusion process of hydrogen from the surface to the bulk of the composites.

Hydrogen production by advanced proton exchange membrane (PEM) water electrolysers—Reduced energy consumption by improved electrocatalysis

Proton exchange membrane (PEM) water electrolysis systems offers several advantages over traditional technologies including greater energy efficiency, higher production rates, and more compact design. Normally in these systems, the anode has the largest overpotential at typical operating current densities. By development of the electrocatalytic material used for the oxygen evolving electrode, great improvements in efficiency can be made. We find that using cyclic voltammetry and steady state polarisation analysis, enables us to separate the effects of true specific electrocatalytic activity and active surface area. Understanding these two factors is critical in developing better electrocatalytic materials in order to further improve the performance of PEM water electrolysis cells. The high current performance of a PEM water electrolysis cell using these oxides as the anode electrocatalyst has also been examined by steady state polarisation measurements and electrochemical impedance spectroscopy. Overall the best cell voltage obtained is 1.567 V at 1 A cm−2 and 80 °C was achieved when using Nafion 115 as the electrolyte membrane.

Microstructural Changes of Membrane Electrode Assemblies during PEFC Durability Testing at High Humidity Conditions

Morphological changes occurring in membrane electrode assemblies (MEAs) were monitored using transmission electron microscopy (TEM) during the course of life testing of polymer electrolyte fuel cells (PEFCs). In the fresh catalyst layers, anode Pt particles were found to have smaller particle sizes, better dispersion, and less agglomeration on the carbon-support surfaces than did the cathode alloy particles. The operation-induced agglomeration of catalyst particles was evaluated for both the anode and cathode after defined life testing periods. Agglomeration of catalyst particles occurred primarily during the first 500 h of testing, which was confirmed by both TEM analysis and electrocatalytic surface area measurement. After 500 h, degradation of the recast Nafion ionomer network within the catalyst layers likely contributes more significantly to MEA performance degradation. Migration of metal catalyst particles toward the interface between the catalyst layer and membrane was observed at both electrodes. The Pt anode catalyst was less stable than the cathode catalyst under high current density and high humidity conditions, which was confirmed by the higher extent of migration observed for the pure Pt than for the . Some Pt particles (from both electrodes) were found to migrate into the membrane during the testing period.