Ga/HZSM-5分子筛上乙烯二聚反应的理论研究
应用理论计算方法研究了Ga/HZSM-5及Al/HZSM-5分子筛上乙烯二聚生成1-丁烯的反应历程,比较了分子筛酸性对反应能量的影响.计算采用分为两层的76T簇模型,应用量子力学和分子力学联合的ONIOM2（B3LYP/6-31G（d,p）：UFF）方法.乙烯二聚过程可按照分步机理和协同机理进行,均得到表面丁基烷氧中间产物.计算结果表明,与在Al/HZSM-5分子筛上的反应过程相比,乙烯在Ga/HZSM-5分子筛上的吸附能低20.62kJ·mol-1,但质子化反应的活化能只高出1.26kJ·mol-1;而乙基烷氧中间体与乙烯分子结合过程的活化能高出62.55kJ·mol-1,原因是Ga原子半径...
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| Published in | 物理化学学报 Vol. 27; no. 6; pp. 1393 - 1399 |
|---|---|
| Main Author | |
| Format | Journal Article |
| Language | Chinese |
| Published |
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
2011
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| Subjects | |
| Online Access | Get full text |
| ISSN | 1000-6818 |
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| Abstract | 应用理论计算方法研究了Ga/HZSM-5及Al/HZSM-5分子筛上乙烯二聚生成1-丁烯的反应历程,比较了分子筛酸性对反应能量的影响.计算采用分为两层的76T簇模型,应用量子力学和分子力学联合的ONIOM2（B3LYP/6-31G（d,p）：UFF）方法.乙烯二聚过程可按照分步机理和协同机理进行,均得到表面丁基烷氧中间产物.计算结果表明,与在Al/HZSM-5分子筛上的反应过程相比,乙烯在Ga/HZSM-5分子筛上的吸附能低20.62kJ·mol-1,但质子化反应的活化能只高出1.26kJ·mol-1;而乙基烷氧中间体与乙烯分子结合过程的活化能高出62.55kJ·mol-1,原因是Ga原子半径大,降低了六元环过渡态的稳定性.若按协同机理,质子转移和C―C键聚合同时进行,在Ga/HZSM-5分子筛上的活化能较Al/HZSM-5的高16.44kJ·mol-1.因此乙烯二聚按照协同机理有利.研究还表明,表面丁基烷氧中间体脱质子,生成1-丁烯并吸附在复原的分子筛酸性位上.该反应在两种酸中心上的活化能几乎相同,但明显高于其他各步的活化能,因此成为整个反应的速度控制步骤. |
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| AbstractList | O641%O643; 应用理论计算方法研究了Ga/HZSM-5及Al/HZSM-5分子筛上乙烯二聚生成1-丁烯的反应历程,比较了分子筛酸性对反应能量的影响.计算采用分为两层的76T簇模型.应用量子力学和分子力学联合的ONIOM2(B3LYP/6-31G(d,p):UFF)方法.乙烯二聚过程可按照分步机理和协同机理进行,均得到表面丁基烷氧中间产物.计算结果表明,与在Al,HZSM-5分子筛上的反应过程相比,乙烯在Ga/HZSM-5分子筛上的吸附能低20.62 kJ·mol-1,但质子化反应的活化能只高出1.26 kJ·mol-1;而乙基烷氧中间体与乙烯分子结合过程的活化能高出62.55 kJ·mol-1,原因是Ga原子半径大,降低了六元环过渡态的稳定性.若按协同机理,质子转移和C-C键聚合同时进行,在Ga/HZSM-5分子筛上的活化能较Al/HZSM-5的高16.44 kJ·mol-1.因此乙烯二聚按照协同机理有利.研究还表明,表面丁基烷氧中间体脱质子,生成1-丁烯并吸附在复原的分子筛酸性位上.该反应在两种酸中心上的活化能几乎相同,但明显高于其他各步的活化能,因此成为整个反应的速度控制步骤. 应用理论计算方法研究了Ga/HZSM-5及Al/HZSM-5分子筛上乙烯二聚生成1-丁烯的反应历程,比较了分子筛酸性对反应能量的影响.计算采用分为两层的76T簇模型,应用量子力学和分子力学联合的ONIOM2（B3LYP/6-31G（d,p）：UFF）方法.乙烯二聚过程可按照分步机理和协同机理进行,均得到表面丁基烷氧中间产物.计算结果表明,与在Al/HZSM-5分子筛上的反应过程相比,乙烯在Ga/HZSM-5分子筛上的吸附能低20.62kJ·mol-1,但质子化反应的活化能只高出1.26kJ·mol-1;而乙基烷氧中间体与乙烯分子结合过程的活化能高出62.55kJ·mol-1,原因是Ga原子半径大,降低了六元环过渡态的稳定性.若按协同机理,质子转移和C―C键聚合同时进行,在Ga/HZSM-5分子筛上的活化能较Al/HZSM-5的高16.44kJ·mol-1.因此乙烯二聚按照协同机理有利.研究还表明,表面丁基烷氧中间体脱质子,生成1-丁烯并吸附在复原的分子筛酸性位上.该反应在两种酸中心上的活化能几乎相同,但明显高于其他各步的活化能,因此成为整个反应的速度控制步骤. |
| Author | 李惊鸿 周丹红 任珏 |
| AuthorAffiliation | 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 |
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| Author_FL | LI Jing-Hong ZHOU Dan-Hong REN Jue |
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| DocumentTitleAlternate | Theoretical Study of Ethylene Dimerization on the Ga/HZSM-5 Zeolite |
| DocumentTitle_FL | Theoretical Study of Ethylene Dimerization on the Ga/HZSM-5 Zeolite |
| EndPage | 1399 |
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| Keywords | Ga/HZSM-5 乙烯二聚 反应机理 密度泛函理论 |
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| Notes | 11-1892/06 Ga/HZSM-5; Ethylene dimerization; Reaction mechanism; Density functional theory We studied the reaction mechanisms of ethylene dimerization to 1-butene on Ga/HZSM-5 and Al/HZSM-5 zeolite catalysts by theoretical calculations and investigated the influence of zeolite acidity on the reaction energetics. The calculations were performed using the hybrid ONIOM2 （B3LYP/6-31G（d, p）：UFF） method based on the two-layered 76T cluster model. Ethylene dimerization may proceed along two different pathways： either a stepwise or a concerted mechanism, and both produce a surface butoxide intermediate. Our results indicated that with respect to the reactions on Al/HZSM-5, the adsorption energy of ethylene on Ga/HZSM-5 was 20.62 kJ·mol-1 lower, and the activation energy for the protonation process was only 1.26 kJ·mol-1 higher. Additionally, the activation energy for a combination of ethoxide intermediate with ethylene was 62.55 kJ·mol-1 higher because of the larger atomic radius of Ga, which led to an unstable six-mem |
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| PublicationTitle | 物理化学学报 |
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| PublicationYear | 2011 |
| Publisher | 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 |
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| Snippet | 应用理论计算方法研究了Ga/HZSM-5及Al/HZSM-5分子筛上乙烯二聚生成1-丁烯的反应历程,比较了分子筛酸性对反应能量的影响.计算采用分为两层的76T簇模型,应用量子力学和分子... O641%O643; 应用理论计算方法研究了Ga/HZSM-5及Al/HZSM-5分子筛上乙烯二聚生成1-丁烯的反应历程,比较了分子筛酸性对反应能量的影响.计算采用分为两层的76T簇模型.应用量子... |
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| SubjectTerms | Ga/HZSM-5 乙烯二聚 反应机理 密度泛函理论 |
| Title | Ga/HZSM-5分子筛上乙烯二聚反应的理论研究 |
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