Phenomena called surface explosions have been reported for decomposition reactions on single crystals, and have been identified by the use of desorption methods. In particular, in TPD, they are manifested by extremely narrow peaks (as little as 3 K in width) and a desorption rate which increases with time in isothermal experiments. In this paper we report such observations for acetate species on Rh single crystals, but extend this to show for the first time that such effects are not restricted to single crystal/UHV experiments, but can also be found on a Rh/Al2O3 catalyst under ambient pressure conditions. These reactions can be classified as second order autocatalytic surface processes, where free surface Rh sites are an essential component of the reaction. It is shown that coadsorbed adatoms are also essential for such explosions to be seen and their role is proposed to be that of a template layer acting to order the acetate in self-poisoning configurations. 相似文献
The role of La2O3 loading in Pd/Al2O3-La2O3 prepared by sol–gel on the catalytic properties in the NO reduction with H2 was studied. The catalysts were characterized by N2 physisorption, temperature-programmed reduction, differential thermal analysis, temperature-programmed oxidation and temperature-programmed desorption of NO.
The physicochemical properties of Pd catalysts as well as the catalytic activity and selectivity are modified by La2O3 inclusion. The selectivity depends on the NO/H2 molar ratio (GHSV = 72,000 h−1) and the extent of interaction between Pd and La2O3. At NO/H2 = 0.5, the catalysts show high N2 selectivity (60–75%) at temperatures lower than 250 °C. For NO/H2 = 1, the N2 selectivity is almost 100% mainly for high temperatures, and even in the presence of 10% H2O vapor. The high N2 selectivity indicates a high capability of the catalysts to dissociate NO upon adsorption. This property is attributed to the creation of new adsorption sites through the formation of a surface PdOx phase interacting with La2O3. The formation of this phase is favored by the spreading of PdO promoted by La2O3. DTA shows that the phase transformation takes place at temperatures of 280–350 °C, while TPO indicates that this phase transformation is related to the oxidation process of PdO: in the case of Pd/Al2O3 the O2 uptake is consistent with the oxidation of PdO to PdO2, and when La2O3 is present the O2 uptake exceeds that amount (1.5 times). La2O3 in Pd catalysts promotes also the oxidation of Pd and dissociative adsorption of NO mainly at low temperatures (<250 °C) favoring the formation of N2. 相似文献
为了探讨超声波灭菌作用机制,进一步为超声波用于净水厂污泥无害化处理提供技术支持,试验采用实验室模拟水样,研究了超声功率(250~1 500 W)、频率(25 k Hz和40 k Hz)对大肠菌群灭活效果、超声空化强度和羟基自由基产量的影响.结果表明:相同时间和频率下,在超声功率为250~1 500 W时,大肠菌群灭活率随着功率的增大先逐渐上升,达到1 250 W后,灭活效果变化不明显;相同时间和功率条件下,40 k Hz灭活效果优于25 k Hz.超声空化强度和羟基自由基的产量与灭活率规律相似,超声灭活率随着超声过程中超声空化强度和羟基自由基产量的增大而增大.通过投加自由基掩蔽剂碳酸氢钠(Na HCO3)掩蔽自由基氧化作用判定羟基自由基在超声灭菌过程中的确产生了灭活作用,但作用比较弱. 相似文献