Selective oxidation of cyclohexene through gold functionalized silica monolith microreactors

SURFACE SCIENCE

卷:646

Article

Alotaibi, Mohammed T.¹  Taylor, Martin J.^1,2,3  Liu, Dan¹  Beaumont, Simon K.⁴  Kyriakou, Georgios^1,2,3 

[1] Univ Hull, Dept Chem, Cottingham Rd, Kingston Upon Hull HU6 7RX, N Humberside, England

[2] Aston Univ, European Bioenergy Res Inst, Birmingham B4 7ET, W Midlands, England

[3] Aston Univ, Chem Engn & Appl Chem, Birmingham B4 7ET, W Midlands, England

[4] Univ Durham, Dept Chem, South Rd, Durham DH1 3LE, England

关键词: Monolith;    Selective oxidation;    Cyclohexene;    Epoxidation;    Gold;   

DOI  :  10.1016/j.susc.2015.10.039

来源: Elsevier

【 摘 要 】

Two simple, reproducible methods of preparing evenly distributed Au nanoparticle containing mesoporous silica monoliths are investigated. These Au nanoparticle containing monoliths are subsequently investigated as flow reactors for the selective oxidation of cyclohexene. In the first strategy, the silica monolith was directly impregnated with Au nanoparticles during the formation of the monolith. The second approach was to pre-functionalize the monolith with thiol groups tethered within the silica mesostructure. These can act as evenly distributed anchors for the Au nanoparticles to be incorporated by flowing a Au nanoparticle solution through the thiol functionalized monolith. Both methods led to successfully achieving even distribution of Au nanoparticles along the length of the monolith as demonstrated by ICP-OES. However, the impregnation method led to strong agglomeration of the Au nanoparticles during subsequent heating steps while the thiol anchoring procedure maintained the nanoparticles in the range of 6.8 +/- 1.4 nm. Both Au nanoparticle containing monoliths as well as samples with no Au incorporated were tested for the selective oxidation of cyclohexene under constant flow at 30 degrees C The Au free materials were found to be catalytically inactive with Au being the minimum necessary requirement for the reaction to proceed. The impregnated Au-containing monolith was found to be less active than the thiol functionalized Au-containing material, attributable to the low metal surface area of the Au nano particles. The reaction on the thiol functionalized Au-containing monolith was found to depend strongly on the type of oxidant used: tert-butyl hydroperoxide (TBHP) was more active than H2O2, likely due to the thiol induced hydrophobicity in the monolith. (C) 2015 Elsevier B.V. All rights reserved.

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