Nano-crystalline tungsten carbide thin films were fabricated on graphite substrates by plasma enhanced chemical vapour deposition in H2 and Ar atmosphere, using WF6 and CH4 as precursors. The crystal phase, structure and chemical components of the films were characterized with X-ray diffraction(XRD), scanning electron microscopy (SEM) and energy-dispersive spectrometer (EDS), respectively. The results showed that the film prepared at CH4/WF6 concentration ratio of 20, working pressure of 100Pa and temperature of 800℃ were composed of sphere particles with a diameter of 20-35nm Electrochemical investigations show that the electrochemical surface area of electrode of the film was large.The electrode of the film exhibited higher electro-catalytic activity in the reaction of methanol oxidation, and its catalytic properties were similar to those of Pt or Pt group catalysts. The constant current of the film catalyst was 123.6mA·cm-2 in the mixture solution of H2SO4 and CH3OH at the concentration of 0.5 mol·L-1 and 2.0 mol·L-1 respectively at 70℃, and its constant potential was only 0. 306V(vs. SCE).
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