Efficient epoxidation over dinuclear sites in titanium silicalite-1

催化作用 环氧丙烷 化学 烯烃纤维 密度泛函理论 活动站点 过氧化氢 沸石 材料科学 光化学 无机化学 计算化学 有机化学 聚合物 环氧乙烷 共聚物
作者
Christopher P. Gordon,Hauke Engler,Amadeus Samuel Tragl,Milivoj Plodinec,Thomas Lunkenbein,Albrecht Berkessel,J. Henrique Teles,Andrei‐Nicolae Parvulescu,Christophe Copéret
出处
期刊:Nature [Nature Portfolio]
卷期号:586 (7831): 708-713 被引量:230
标识
DOI:10.1038/s41586-020-2826-3
摘要

Titanium silicalite-1 (TS-1) is a zeolitic material with MFI framework structure, in which 1 to 2 per cent of the silicon atoms are substituted for titanium atoms. It is widely used in industry owing to its ability to catalytically epoxidize olefins with hydrogen peroxide (H2O2), leaving only water as a byproduct1,2; around one million tonnes of propylene oxide are produced each year using this process3. The catalytic properties of TS-1 are generally attributed to the presence of isolated Ti(iv) sites within the zeolite framework1. However, despite almost 40 years of experimental and computational investigation4–10, the structure of these active Ti(iv) sites is unconfirmed, owing to the challenges of fully characterizing TS-1. Here, using a combination of spectroscopy and microscopy, we characterize in detail a series of highly active and selective TS-1 propylene epoxidation catalysts with well dispersed titanium atoms. We find that, on contact with H217O2, all samples exhibit a characteristic solid-state 17O nuclear magnetic resonance signature that is indicative of the formation of bridging peroxo species on dinuclear titanium sites. Further, density functional theory calculations indicate that cooperativity between two titanium atoms enables propylene epoxidation via a low-energy reaction pathway with a key oxygen-transfer transition state similar to that of olefin epoxidation by peracids. We therefore propose that dinuclear titanium sites, rather than isolated titanium atoms in the framework, explain the high efficiency of TS-1 in propylene epoxidation with H2O2. This revised view of the active-site structure may enable further optimization of TS-1 and the industrial epoxidation process. A combination of spectroscopy, microscopy and theoretical calculations shows that the reactivity of titanium silicalite-1 as an epoxidation catalyst is due to the presence of dinuclear titanium sites.
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