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碳模板介孔氧化铝的表面化学

Surface chemistry of carbon-templated mesoporous aluminas.

作者信息

Onfroy Thomas, Li Wen-Cui, Schüth Ferdi, Knözinger Helmut

机构信息

Department Chemie und Biochemie, Universität München, Butenandtstr., 5-13 E, D-81377, München, Germany.

出版信息

Phys Chem Chem Phys. 2009 May 21;11(19):3671-9. doi: 10.1039/b821505g. Epub 2009 Mar 23.

Abstract

Using infrared spectroscopy, a comparative investigation was carried out of the surface properties of mesoporous aluminas prepared by the carbon templating route and of a commercial alumina PURAL SB. In the hydroxylated state the mesoporous materials bear surface OH groups terminally bonded to an octahedral Al3+ ion, which has basic properties. In contrast, the surface of the commercial oxide additionally exposes OH groups which are terminally bonded to a tetrahedral cation. Bridging OH groups are Brønsted acid sites and are present on both oxides. The sites on the reference sample are stronger protonic acid sites than those on the mesoporous oxide. The strongest Brønsted acid sites are triply bridging OH groups, which are relatively more abundant on the reference oxide. Structural protons in the bulk of the oxides are also present on both oxides; they seem to be somewhat more stable in the reference sample. Condensation of basic OH groups with acidic groups at increasing dehydroxylation temperatures creates Lewis acid sites in the form of coordinatively unsaturated (cus) Al3+ ions the acid strength of which is higher on the reference material than on the mesoporous oxide. In conclusion, the surface properties of the investigated oxides are strongly dependent on the preparation route and conditions.

摘要

采用红外光谱法,对通过碳模板法制备的介孔氧化铝和商业氧化铝PURAL SB的表面性质进行了对比研究。在羟基化状态下,介孔材料带有末端键合到八面体Al³⁺离子上的表面羟基,该八面体Al³⁺离子具有碱性。相比之下,商业氧化物的表面还暴露有末端键合到四面体阳离子上的羟基。桥连羟基是布朗斯特酸位点,在两种氧化物上均存在。参比样品上的位点是比介孔氧化物上的位点更强的质子酸位点。最强的布朗斯特酸位点是三重桥连羟基,在参比氧化物上相对更为丰富。两种氧化物的本体中也都存在结构质子;它们在参比样品中似乎更稳定一些。在不断升高的脱羟基温度下,碱性羟基与酸性基团的缩合形成了配位不饱和(cus)Al³⁺离子形式的路易斯酸位点,其酸强度在参比材料上高于介孔氧化物。总之,所研究氧化物的表面性质强烈依赖于制备路线和条件。

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