TS-1/H2O2分子筛体系溶剂效应及活性中心预测的理论计算
Insights into the Solvent Effects and Active Center Identification for TS-1/H2O2 Zeolite: A Computational Study
DOI: 10.12677/hjcet.2026.161006, PDF,    科研立项经费支持
作者: 李蒙召*, 李 慧, 杨 志：长治学院化学系，山西 长治；谢泽民：朔州市大医院医学装备科，山西 朔州
关键词: TS-1分子筛；密度泛函理论；钛氧活性中心；溶剂效应；烯烃环氧化 ；TS-1 Zeolite； DFT； Ti-Hydroperoxo Intermediates； Solvent Effects； Olefin Epoxidation
摘要: TS-1/H2O2分子筛催化体系因其反应条件温和、原子经济性高等环境友好的特点，已成为绿色化学领域的关键技术之一，但关于其微观活性中心的确切结构、溶剂分子的微观作用机制，仍是当前理论研究的核心。本研究采用密度泛函理论方法，在B3LYP/6-31G (d, p)理论水平下，系统探究了溶剂分子(H2O, CH3OH)对TS-1/H2O2体系的影响及钛氧活性中间体的形成。计算结果表明，在T10和T8位上，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)。溶剂分子可通过直接与钛中心作用形成六配位络合物，或通过氢键作用被吸附，其中对Ti-η1(OOH)中间体的稳定化作用更强。进一步的丙烯环氧化机理研究表明，具有三元环结构的Ti-η2(OOH)活性中心在反应中断/成键数目更少，其对应的反应能垒更低，表现出更高的催化活性。本研究从原子尺度揭示了TS-1/H2O2体系的溶剂效应与活性中心特性，为理性设计高效钛硅分子筛催化剂提供了理论依据。
Abstract: The TS-1/H2O2 zeolite catalytic system has emerged as one of the key technologies in green chemistry due to its environmentally friendly features, such as mild reaction conditions and high atom economy. However, the exact structure of its microscopic active centers and the detailed mechanism underlying the role of solvent molecules remain central topics in current theoretical research. In this study, the effects of solvent molecules (H2O, CH3OH) on TS-1/H2O2 zeolite and the formation of titanium-hydroperoxo intermediates was investigated using density functional theory (DFT) at B3LYP/6-31G (d, p) level. The calculation results show that at the T10 and T8 sites, the framework Ti interacts with H2O2 to form two titanium-oxygen active intermediates, namely the five-membered ring Ti-η1(OOH) and the three-membered ring Ti-η2(OOH). Solvent molecules can stabilize the active intermediates by either directly acting with the Ti center to form six-coordinate complexes or being adsorbed via hydrogen-bonding, with a more pronounced stabilizing effect on the Ti-η1(OOH) intermediate. Further studies on the mechanism of propylene epoxidation showed that the Ti-η2(OOH) active sites with a three-membered ring structure had fewer interruptions/bonds in the reaction, and the corresponding reaction energy barrier was lower, which showed higher catalytic activity. This study reveals the solvent effect and active center characteristics of TS-1/H2O2 zeolite from the atomic scale, which provides a theoretical basis for the rational design of high efficiency titanium silicalite catalysts.
文章引用：李蒙召, 李慧, 杨志, 谢泽民. TS-1/H2O2分子筛体系溶剂效应及活性中心预测的理论计算[J]. 化学工程与技术, 2026, 16(1): 52-63. https://doi.org/10.12677/hjcet.2026.161006

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