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Effect of Li2O doping on the surface and catalytic properties of NiO solid

机译:Li2O掺杂对NiO固体表面和催化性能的影响

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The influence of Li2O treatment (0.19-0.75 mol%) on the surface and catalytic properties of NiO were investigated using nitrogen adsorption at -196°C and the catalytic decomposition of H2O2 at 30-50°C. Pure and treated solid samples were subjected to thermal treatment at 300°C, 500°C and 700°C, respectively. The results obtained revealed that Li2O treatment of NiO solid brought about a measurable decrease (30-63%) in its BET surface area, SBET, and a decrease of 20-44% in its total pore volume, Vp, especially for the solid samples calcined at 700°C. The observed decrease in the SBET value of NiO due to treatment with Li2O was attributed to transformation of some of the Ni2+ ions into Ni3+ ions with a subsequent contraction in the lattice and also to pore widening. The catalytic activities of all the doped catalyst samples investigated showed that their catalytic activity was smaller than that measured for the untreated samples. The catalytic activity, expressed as the reaction rate constant per unit surface area (k), was effectively decreased by the doping process. Although this process increased the number of Ni3+ ions, it decreased the activity of the treated solids because of the formation of Li+-Ni3+ ion pairs which could not readily exchange electrons with the reacting substrate (H2O2). The formation of such ion pairs may take place at sites associated with the most active Ni2+ ions. The doping process did not modify the mechanism of the catalytic reaction but decreased the concentration of active sites involved in the catalysis of H2O2 decomposition without changing their energetic nature.
机译:研究了Li2O处理(0.19-0.75 mol%)对NiO的表面和催化性能的影响,方法是在-196°C下用氮吸附,然后在30-50°C下用H2O2催化分解。将纯净和经过处理的固体样品分别在300°C,500°C和700°C下进行热处理。所获得的结果表明,Li2O处理的NiO固体导致其BET表面积SBET显着降低(30-63%),并且其总孔体积Vp降低20-44%,特别是对于固体样品在700°C下煅烧。观察到的由于用Li2O处理而导致的NiO的SBET值降低,这归因于一些Ni2 +离子转变为Ni3 +离子,随后晶格收缩,也归因于孔扩大。研究的所有掺杂催化剂样品的催化活性表明它们的催化活性小于未处理样品的催化活性。通过掺杂过程有效降低了催化活性,表示为每单位表面积(k)的反应速率常数。尽管此过程增加了Ni3 +离子的数量,但由于形成了Li + -Ni3 +离子对,该离子对不易与反应基质(H2O2)交换电子,因此降低了处理过的固体的活性。此类离子对的形成可能发生在与活性最高的Ni2 +离子相关的位置。掺杂过程没有改变催化反应的机理,但是降低了H 2 O 2分解催化中涉及的活性位点的浓度,而没有改变它们的能量性质。

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