ABSTRACT
Magnetron sputtering was employed for the deposition of cobalt oxide thin films on stainless steel meshes. Catalysts prepared by sputtering in inert and oxidation atmosphere were compared with those obtained by electrochemical deposition and hydrothermal synthesis. Systematic characterization using X-ray diffraction, scanning electron microscopy, N2 physisorption, infrared spectroscopy, Raman spectroscopy, and temperature-programmed reduction by hydrogen allowed detailed monitoring of their physicochemical properties. Ethanol gas-phase oxidation was employed as a model reaction to reveal the catalytic performance of the catalysts. It was shown that the catalyst prepared by magnetron sputtering in oxidation atmosphere exhibited the best mechanical stability among all studied catalysts. Moreover, its catalytic activity was 18 times higher than that of pelletized commercial cobalt oxide.
Subject(s)
Cobalt , Oxides , Volatile Organic Compounds , CatalysisABSTRACT
Hematite, α-Fe2O3, is considered as one of the most promising materials for sustainable hydrogen production via photoelectrochemical water splitting with a theoretical solar-to-hydrogen efficiency of 17%. However, the poor electrical conductivity of hematite is a substantial limitation reducing its efficiency in real experimental conditions. Despite of computing models suggesting that the electrical conductivity is extremely anisotropic, revealing up to 4 orders of magnitude higher electron transport with conduction along the (110) hematite crystal plane, synthetic approaches allowing the sole growth in that direction have not been reported yet. Here, we present a strategy for controlling the crystal orientation of very thin hematite films by adjusting energy of ion flux during advanced pulsed reactive magnetron sputtering technique. The texture and effect of the deposition mode on the film properties were monitored by XRD, conversion electron Mössbauer spectroscopy, XPS, SEM, AFM, PEC water splitting, IPCE, transient photocurrent measurements, and Mott-Schottky analysis. The precise control of the synthetic conditions allowed to fabricate hematite photoanodes exhibiting fully textured structures along (110) and (104) crystal planes with huge differences in photocurrents of 0.65 and 0.02 mA cm(-2) (both at 1.55 V versus RHE), respectively. The photocurrent registered for fully textured (110) film is among record values reported for thin planar films. Moreover, the developed fine-tuning of crystal orientation having a huge impact on the photoefficiency would induce further improvement of thin hematite films mainly if cation doping will be combined with the controllable texture.
