Use of Short Time-on-Stream Attenuated Total Internal Reflection Infrared Spectroscopy To Probe Changes in Adsorption Geometry for Determination of Selectivity in the Hydrogenation of Citral

被引：38
作者：
Daly, H. [1 ]
Manyar, H. G. [1 ]
Morgan, R. [1 ]
Thompson, J. M. [1 ]
Delgado, J. -J. [2 ]
Burch, R. [1 ]
Hardacre, C. [1 ]
机构：
[1] Queens Univ Belfast, Sch Chem & Chem Engn, CenTACat, Belfast BT9 5AG, Antrim, North Ireland
[2] Univ Cadiz, Dept Ciencia Mat & Ingn Mmet & Quim Inorgan, Cadiz, Spain
来源：
ACS CATALYSIS | 2014年 / 4卷 / 08期
基金：
英国工程与自然科学研究理事会;
关键词：
Pt; ATR; infrared; citral; hydrogenation; SITU ATR-IR; LIQUID-PHASE HYDROGENATION; ALPHA; BETA-UNSATURATED ALDEHYDES; UNSATURATED ALDEHYDES; ASYMMETRIC HYDROGENATION; 1ST PRINCIPLES; PTSN CATALYSTS; BENZYL ALCOHOL; PD/AL2O3; OXIDATION;
D O I：
10.1021/cs500185n
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：
A new experimental procedure based on attenuated total reflection infrared spectroscopy has been developed to investigate surface species under liquid phase reaction conditions. The technique has been tested by investigating the enhanced selectivity in the hydrogenation of alpha,beta-unsaturated aldehyde citral over a 596 Pt/SiO2 catalyst toward unsaturated alcohols geraniol/nerol, which occurs when citronellal is added to the reaction. The change in selectivity is proposed to be the result of a change in the citral adsorption mode in the presence of citronellal. Short time on stream attenuated total internal reflection infrared spectroscopy has allowed identification of the adsorption modes of citral. With no citronellal, citral adsorbs through both the C=C and C=O groups; however, in the presence of citronellal, citral adsorption occurs through the C=O group only, which is proposed to be the cause of the altered reaction selectivity.
引用
收藏
页码：2470 / 2478
页数：9
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