Shape-dependence of the thermal and photochemical reactions of methanol on nanocrystalline anatase TiO2

被引:22
作者
Bennett, David A. [1 ]
Cargnello, Matteo [2 ]
Diroll, Benjamin T. [3 ,4 ]
Murray, Christopher B. [3 ]
Vohs, John M. [1 ]
机构
[1] Univ Penn, Dept Biomol & Chem Engn, Philadelphia, PA 19104 USA
[2] Stanford Univ, Dept Chem Engn, Stanford, CA 94305 USA
[3] Univ Penn, Dept Chem, Philadelphia, PA 19104 USA
[4] Argonne Natl Lab, Ctr Nanoscale Mat, Lemont, IL 60439 USA
关键词
Anatase; TiO2; TPD; Methanol; Photo-oxidation; SINGLE-CRYSTAL SURFACES; OXIDE SURFACES; PHOTOCATALYTIC ACTIVITY; ALIPHATIC-ALCOHOLS; SITE REQUIREMENTS; CARBOXYLIC-ACIDS; MATERIALS GAP; THIN-FILMS; ADSORPTION; TIO2(001);
D O I
10.1016/j.susc.2016.07.009
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Structure-activity relationships and the influence of particle size and shape on the partial-and photo-oxidation of methanol on nanocrystalline anatase TiO2 were investigated using temperature-programmed desorption. The study employed two distinct nano particle morphologies: truncated bipyramids exposing primarily {101} facets, and flatter platelets exposing primarily {001} surfaces, whose nominal sizes ranged from 10 to 25 nm. The platelets were found to be more active for thermally-driven reactions, such as coupling of methoxide groups to produce dimethyl ether, and deoxygenation to produce methane. A dependence of the reactivity of {001} facets for the coupling of methoxide groups to produce dimethyl ether on facet size was also observed. In contrast to the thermally-driven reactions, the bipyramidal nanoparticles were observed to be more active for a range of photochemical reactions, including oxidation and coupling to produce methyl formate, and photo decomposition of surface methoxide species. This study also shows how well-defined nanocrystals can be used to help bridge the materials gap between studies of single crystal model catalysts and their high surface area industrial analogs. (C) 2016 Elsevier B.V. All rights reserved.
引用
收藏
页码:1 / 7
页数:7
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