DFT quantum chemical modeling of the interaction of alkenes with Cu+ sites in zeolites

被引：13

作者：

Broclawik, E.

Rejmak, P.

Kozyra, P.

Datka, J.

机构：

[1] Polish Acad Sci, Inst Catalysis & Surface Chem, PL-30239 Krakow, Poland

[2] Tohoku Univ, New Ind Creat Hatchery Ctr, Aoba Ku, Sendai, Miyagi 9808579, Japan

[3] Jagiellonian Univ, Fac Chem, PL-30060 Krakow, Poland

来源：

CATALYSIS TODAY | 2006年 / 114卷 / 2-3期

关键词：

alkene activation; IR spectra; copper active sites; CuZSM-5; DFT modeling;

D O I：

10.1016/j.cattod.2006.01.015

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

In this work charge transfer phenomenon between the admolecule and the active site and its consequences for the bond weakening/strengthening in the adsorbed molecule are discussed on the example of unsaturated hydrocarbons (early alkenes) interacting with Cu+ cation embedded in a model of ZSM-5 zeolitic site. Detailed comparison of ethene interaction with various metallic sites based on this work and comparative analysis of other related studies helps to formulate working rules of charge transfer decomposition and interpretation. All studied alkenes form strongly bonded pi complexes and become strongly activated on Cu+ sites in ZSM-5 by both processes: IT donation and pi* backdonation, what clarifies the mechanism by which the activation of the C=C bond in alkenes adsorbed on Cu(+)ZSM-5 takes place. Calculated shifts in C=C stretching frequencies qualitatively follow the experiment and are a good measure of the activation. (c) 2006 Elsevier B.V. All rights reserved.

引用

页码：162 / 168

页数：7

共 26 条

[1] T-O-T skeletal vibration in CuZSM-5 zeolite: IR study and quantum chemical modeling [J].