Ti-MWW分子筛钛氧活性中心与溶剂分子吸附作用的理论研究

引用本文: 邹晶, 范志琳, 姜丽莎, 周丹红. Ti-MWW分子筛钛氧活性中心与溶剂分子吸附作用的理论研究[J]. 物理化学学报, 2016, 32(4): 935-942. doi: 10.3866/PKU.WHXB201601201 shu

Citation: ZOU Jing, FAN Zhi-Lin, JIANG Li-Sha, ZHOU Dan-Hong. Theoretical Study of the Solvent Adsorption on Ti-Peroxo Active Center in Ti-MWW Zeolite[J]. Acta Physico-Chimica Sinica, 2016, 32(4): 935-942. doi: 10.3866/PKU.WHXB201601201 shu

Ti-MWW分子筛钛氧活性中心与溶剂分子吸附作用的理论研究

1.
辽宁师范大学化学化工学院, 辽宁大连 116029

通讯作者: 周丹红

基金项目:
国家自然科学基金(21343010)资助项目 (21343010)

摘要: 采用密度泛函理论方法,研究了钛硅分子筛Ti-MWW与H₂O₂所形成的钛氧活性中间体的结构,以及溶剂分子吸附对其几何结构和电子结构的影响。结果表明,骨架Ti 与H₂O₂作用生成两种钛氧活性中间体,即五元环的Ti-η¹-OOH和三元环的Ti-η²-OOH,骨架Ti 中心可再吸附一个溶剂分子,形成六配位络合物结构,不同溶剂分子的吸附能力为H₂O > CH₃OH > CH₃CN。两种钛氧活性中心与溶剂分子的吸附作用略有不同,表现为Ti-η¹-OOH > Ti-η²-OOH,而Ti 的落位也对吸附效应有很大影响,T1位点的Ti 中心与溶剂分子的吸附作用明显强于T3 位点的Ti 中心。溶剂分子吸附还将影响活性氧的亲电性和催化活性。计算结果表明在Ti-η²-OOH活性中心吸附CH₃CN可降低氯丙烯环氧化反应的活化能。

关键词:

English

Theoretical Study of the Solvent Adsorption on Ti-Peroxo Active Center in Ti-MWW Zeolite

1.
College of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, Liaoning Province, P. R. China

Corresponding author: 周丹红

Received Date: 24 November 2015
Available Online: 20 January 2016
Fund Project:
国家自然科学基金(21343010)资助项目

Abstract: Density functional theory is used to study the structures of the Ti-peroxide species in a Ti-MWW/H₂O₂ system and the influence of the coordination with solvent molecules on the geometries and electronic features. The result indicated that the framework Ti can interact with H₂O₂ to form two kinds of Ti-peroxide species, the five-membered ring Ti-η¹-OOH and the three-membered ring Ti-η²-OOH. The framework Ti center can further interact with solvent molecules of H₂O, CH₃OH, and CH₃CN to form 6-coordinated complexes. The adsorption energies decreased as H₂O > CH₃OH > CH₃CN. Both Ti-peroxide species display different adsorption capacity as Ti-η¹-OOH > Ti-η²-OOH. The location of Ti also has a distinct effect on the adsorption. The central Ti at T1 prefers to adsorb solvent molecule over the Ti at T3. In addition, solvent adsorption also influences the electrophilicity of the active oxygen atom. The calculated results indicate that on the Ti-η²-OOH active center with adsorbed CH₃CN, the activation energy of the epoxidation of chloropropene has been reduced.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

Ti-MWW分子筛钛氧活性中心与溶剂分子吸附作用的理论研究

通讯作者: 周丹红

English

Theoretical Study of the Solvent Adsorption on Ti-Peroxo Active Center in Ti-MWW Zeolite

Corresponding author: 周丹红

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Ti-MWW分子筛钛氧活性中心与溶剂分子吸附作用的理论研究

通讯作者: 周丹红

English

Theoretical Study of the Solvent Adsorption on Ti-Peroxo Active Center in Ti-MWW Zeolite

Corresponding author: 周丹红

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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