Adsorption of various compounds onto nanooxides unmodified and differently pretreated

V. Gun'ko, O. K. Matkovsky
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Abstract

Features of interfacial adsorbate/adsorbent phenomena depend on several factors: particulate morphology, texture, and structure of adsorbents, molecular weight, shape, and polarity of adsorbates; as well as prehistory of adsorbents pretreated under different conditions. All these factors could affect the efficiency of practical applications of not only adsorbents but also polymer fillers, carriers, catalysts, etc. Interactions of nonpolar nitrogen, hexane, benzene, weakly polar acetonitrile, and polar diethylamine, triethylamine, and water with individual (silica, alumina), binary (silica/alumina (SA)) and ternary (alumina/silica/titania, AST) nanooxides were studied using experimental and theoretical methods to elucidate the influence of the morphological and textural characteristics and surface composition of the materials on the adsorption phenomena. The specific surface area SX / ratio (X is an adsorbate) changes from 0.7 for hexane adsorbed onto amorphous silica/alumina SA8 with 8 wt. % Al2O3 (degassed at 200 °C) to 1.9 for acetonitrile adsorbed onto pure fumed alumina (treated at 900 °C). These changes are relatively large because of variations in orientation, lateral interactions, and adsorption compressing of organic molecules interacting with surfaces characterized by certain set and amounts of various active sites, as well as due to changes in the accessibility of pore surface for probe molecules of different sizes. Larger SX / > 1 values are observed for complex fumed oxides with larger primary nanoparticles, greater surface roughness, hydrophilicity, and Brønsted and Lewis acidity of a surface. Both polar and nonpolar adsorbates can change the morphology and texture of aggregates of oxide nanoparticles, e.g., swelling of structures, compacted during various pretreatments, upon the adsorption of liquids. The studied effects should be considered upon practical applications of adsorbents, especially “soft” fumed oxides.
未经改性和不同预处理的纳米氧化物对各种化合物的吸附作用
吸附剂/吸附剂界面现象的特征取决于几个因素:吸附剂的颗粒形态、质地和结构,吸附剂的分子量、形状和极性,以及吸附剂在不同条件下预处理的历史。所有这些因素不仅会影响吸附剂的实际应用效率,还会影响聚合物填料、载体、催化剂等的实际应用效率。利用实验和理论方法研究了非极性氮、正己烷、苯、弱极性乙腈以及极性二乙胺、三乙胺和水与单独(二氧化硅、氧化铝)、二元(二氧化硅/氧化铝 (SA))和三元(氧化铝/二氧化硅/钛,AST)纳米氧化物的相互作用,以阐明材料的形态和质地特征以及表面成分对吸附现象的影响。在含有 8 wt. % Al2O3 的无定形二氧化硅/氧化铝 SA8(在 200 °C 下脱气)上吸附正己烷时,比表面积 SX / 比率(X 为吸附剂)为 0.7,而在纯气相氧化铝(在 900 °C 下处理)上吸附乙腈时,比表面积 SX / 比率为 1.9。这些变化之所以比较大,是因为有机分子在与具有一定数量的各种活性位点的表面相互作用时,在取向、横向相互作用和吸附压缩等方面发生了变化,也是因为孔隙表面对不同大小的探针分子的可及性发生了变化。在原生纳米颗粒较大、表面粗糙度较高、亲水性较强以及表面具有布氏酸性和路易斯酸性的复杂气相氧化物中,可以观察到较大的 SX / > 1 值。极性和非极性吸附剂都能改变氧化物纳米颗粒聚集体的形态和质地,例如,在吸附液体时,在各种预处理过程中压实的结构会膨胀。在实际应用吸附剂,特别是 "软 "气相氧化物时,应考虑所研究的影响。
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