The effect of chloride ions on a monoclinic ZrO2-supported RuOx （RuOx/m-ZrO2） catalyst with a Ru surface density of 0.3 Ru/nm2 was studied in the selective oxidation of methanol to methyl formate （MF） at a low tem...The effect of chloride ions on a monoclinic ZrO2-supported RuOx （RuOx/m-ZrO2） catalyst with a Ru surface density of 0.3 Ru/nm2 was studied in the selective oxidation of methanol to methyl formate （MF） at a low temperature of 373 K. The m-ZrO2 support was Cl-free, and Cl- ions were introduced into the RuOx/m-ZrO2 catalyst by impregnation with zirconium oxychloride or ammonium chloride and subsequent thermal treatment in air at 673 K. The structures of these catalysts were characterized by X-ray diffraction, Raman and X-ray photoelectron spectroscopies. Their reducibility was probed by temperature-programmed reduction in H2. The RuOx domains were present as highly dispersed Rut42- structure on m-ZrO2 with similar reducibility for the RuOx/m-ZrO2 samples irrespective of modification with or without Cl ions. Introduction of appropriate amounts of zirconium oxychloride into RuOx/m-ZrO2 led to a remarkable increase in the methanol oxidation rate and MF selectivity, whereas introduction of ammonium chloride or zirconyl nitrate significantly inhibited the catalytic performance of RuOx/m-ZrO2. The promoting effect of Cl- ions derived from zirconium oxychloride can be tentatively attributed to their roles in facilitating the adsorption of methanol and desorption of MF product or its intermediates. This finding provides novel insights into the promoting effect of Cl- ions on oxides-based catalysts for selective oxidation reactions.展开更多
In order to investigate the effect of lanthanum ion implantation on theoxidation behavior of zircaloy at 500℃, Zircaloy specimens were implanted by lanthanum ions with adose range from 5xl0^(16) to 2xl0^(17) ions/cm^...In order to investigate the effect of lanthanum ion implantation on theoxidation behavior of zircaloy at 500℃, Zircaloy specimens were implanted by lanthanum ions with adose range from 5xl0^(16) to 2xl0^(17) ions/cm^2 at room temperature, and then oxidized at 500℃ for100 min. The valence of the oxides in the scale was analyzed by X-ray Photoelectron Spectroscopy(XPS). The phase structures of the oxides in the scale were examined by Glancing Angle X-rayDiffraction (GAXRD). With the increase of implanted lanthanum ions dose, the phase structures in theoxide scale are transformed from monoclinic zirconia to hexagonal one and then to monoclinic oneagain. The measurement of weight gain showed that a similar change from the decreased gain toincreased one again is achieved in the oxidation behavior of lanthanum ion implanted zircaloycompared with that of as-received zircaloy.展开更多
基金supported by the National Natural Science Foundation of China(20825310 and 20973011)National Basic Research Project of China (2011CB201400 and 2011CB808700)
文摘The effect of chloride ions on a monoclinic ZrO2-supported RuOx （RuOx/m-ZrO2） catalyst with a Ru surface density of 0.3 Ru/nm2 was studied in the selective oxidation of methanol to methyl formate （MF） at a low temperature of 373 K. The m-ZrO2 support was Cl-free, and Cl- ions were introduced into the RuOx/m-ZrO2 catalyst by impregnation with zirconium oxychloride or ammonium chloride and subsequent thermal treatment in air at 673 K. The structures of these catalysts were characterized by X-ray diffraction, Raman and X-ray photoelectron spectroscopies. Their reducibility was probed by temperature-programmed reduction in H2. The RuOx domains were present as highly dispersed Rut42- structure on m-ZrO2 with similar reducibility for the RuOx/m-ZrO2 samples irrespective of modification with or without Cl ions. Introduction of appropriate amounts of zirconium oxychloride into RuOx/m-ZrO2 led to a remarkable increase in the methanol oxidation rate and MF selectivity, whereas introduction of ammonium chloride or zirconyl nitrate significantly inhibited the catalytic performance of RuOx/m-ZrO2. The promoting effect of Cl- ions derived from zirconium oxychloride can be tentatively attributed to their roles in facilitating the adsorption of methanol and desorption of MF product or its intermediates. This finding provides novel insights into the promoting effect of Cl- ions on oxides-based catalysts for selective oxidation reactions.
文摘In order to investigate the effect of lanthanum ion implantation on theoxidation behavior of zircaloy at 500℃, Zircaloy specimens were implanted by lanthanum ions with adose range from 5xl0^(16) to 2xl0^(17) ions/cm^2 at room temperature, and then oxidized at 500℃ for100 min. The valence of the oxides in the scale was analyzed by X-ray Photoelectron Spectroscopy(XPS). The phase structures of the oxides in the scale were examined by Glancing Angle X-rayDiffraction (GAXRD). With the increase of implanted lanthanum ions dose, the phase structures in theoxide scale are transformed from monoclinic zirconia to hexagonal one and then to monoclinic oneagain. The measurement of weight gain showed that a similar change from the decreased gain toincreased one again is achieved in the oxidation behavior of lanthanum ion implanted zircaloycompared with that of as-received zircaloy.
