H_ZSM_5分子筛上的乙烯二聚反应机理的理论计算研究.pdfVIP

29 8 2008 8 Vol. 29 No. 8 Chinese Journal of Catalysis August 2008 :2008) 0807 1505 : 715~ 7 19 HZSM5 张 佳, 周丹红, 倪 丹 ( 辽宁师范大学化学化工学院功能材料化学研究所, 辽宁大连 116029) : ONIOM2( B3LYP/ 631G( d, p) : UFF) HZSM5 . 40T ZSM5 , . , , , . 15288 11945 kJ/ mol, . , , , 16230 kJ/ mol, . . : HZSM5 ; ; ; : O643 : A Investigation on Ethylene Dimerization over HZSM5 Zeolite by Theoretical Calculation ZHANG Jia, ZHOU Danhong* , NI Dan ( Institute of Chemistry f or Functionaliz ed M aterials, College of Chemistry and Chemical Engineering, Liaoning Normal University , Dalian 11 029, L iaoning , China) Abstract: By the QM/ MM hy dride ON IOM2( B3LYP/ 631G( d, p) : UFF) method, the rea tion me hanism of ethylene dimerization over HZSM5 zeolite w as investigated. A 40T luster model w as used to simulate the a idi sites lo ated at the interse tion of hannels in ZSM5 zeolite. Both stepw ise and on erted rea tion path w ays w ere ex amined. For the stepw ise me hanism , the ethylene mole ule w as firstly adsorbed at the Brnsted a id site via hydrogen bonding to form a stable omplex, whi h then went through the protonation, leading to the formation of the ethoxide intermediate. Furthermore, the ethox ide rea ted w ith the se ond ethylene mole ule to form the butoxide produ t. The al ulated a tivation energies for the first and se ond steps w ere 15288 and 11945 kJ/ mol, respe tively. The ethylene protonation step was onfirmed as the ratelimiting step. For the on erted me hanism, the protonation, C- C and C- O bonds formation pro eeded simultaneously to produ e butoxide. The al ulated a tivation energy of 16230 kJ/ mol was slightl