氨基酸辅助合成高活性六配位钛物种的TS-1分子筛

doi:10.1016/S1872-2067(21)63882-2

催化学报 ›› 2021, Vol. 42 ›› Issue (12): 2189-2196.DOI: 10.1016/S1872-2067(21)63882-2

氨基酸辅助合成高活性六配位钛物种的TS-1分子筛

王煜瑶^a, 李莉^a, 白日升^a, 高士钦^a, 冯兆池^c, 张强^a^,^#(), 于吉红^a^,^b^,^*()

^a吉林大学化学学院, 无机合成与制备化学国家重点实验室, 吉林长春130012
^b吉林大学, 未来科学国际合作联合实验室, 吉林长春130012
^c中国科学院大连化学物理研究所, 催化基础国家重点实验室, 辽宁大连116023

收稿日期:2021-05-08 接受日期:2021-05-08 出版日期:2021-12-18 发布日期:2021-07-07
通讯作者: 张强,于吉红
基金资助:
国家自然科学基金(21920102005);国家自然科学基金(21835002);国家自然科学基金(21621001);高等学校学科创新引智计划(B17020)

Amino acid-assisted synthesis of TS-1 zeolites containing highly catalytically active TiO₆ species

Yuyao Wang^a, Li Li^a, Risheng Bai^a, Shiqin Gao^a, Zhaochi Feng^c, Qiang Zhang^a^,^#(), Jihong Yu^a^,^b^,^*()

^aState Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, Jilin, China
^bInternational Center of Future Science, Jilin University, Changchun 130012, Jilin, China
^cState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

Received:2021-05-08 Accepted:2021-05-08 Online:2021-12-18 Published:2021-07-07
Contact: Qiang Zhang,Jihong Yu
About author:# E-mail: qiangz@jlu.edu.cn
* Tel/Fax: +86-431-85168608; E-mail: jihong@jlu.edu.cn;
Supported by:
National Natural Science Foundation of China(21920102005);National Natural Science Foundation of China(21835002);National Natural Science Foundation of China(21621001);111 Project(B17020)

摘要/Abstract

摘要：

TS-1分子筛是以TO₄ (T = Si, Ti)四面体为基本单元, 通过氧桥连接而形成的具有MFI拓扑结构的微孔晶体材料, 其在催化烯烃环氧化、酮类氨肟化、氧化脱硫及芳香烃羟基化等氧化反应中表现出较好的催化活性. 目前, 提高TS-1分子筛催化性能的方法主要包括: (1)制备纳米和多级孔TS-1分子筛, 以提高其扩散传质性能; (2)提高TS-1分子筛的钛含量并抑制锐钛矿相的产生, 以增加其催化活性位点. 最新研究表明, 相比于传统四配位钛物种(TiO₄)作为催化活性中心, 六配位(TiO₆)钛物种在烯烃环氧化反应中具有更高的催化活性, 可进一步降低反应活化能, 最终实现高效催化转化. 然而, TiO₆物种结构中的Ti-OH组分, 易导致开环反应发生, 从而降低环氧化产物的选择性. 因此, 构筑高活性TiO₆物种及调变TiO₄/TiO₆比例, 对提高烯烃转化率及环氧产物选择性具有重要意义. 当前, 高活性钛物种的结构表征及其构筑已成为研究热点且仍面临挑战.

本文协同采用氨基酸辅助合成策略和两步晶化方法, 成功地制备出具有TiO₄和TiO₆物种且无锐钛矿相的多级孔TS-1分子筛. 在该协同策略中, 两步晶化过程有利于抑制锐钛矿相的形成, 而氨基酸的引入对高活性TiO₆物种的构筑具有重要作用. 氨基酸分子可与钛原料形成螯合物, 为TS-1分子筛晶化提供“养料”, 并有效平衡晶体成核与生长速率及稳定TiO₆物种, 最终实现制备富含TiO₆物种的多级孔TS-1分子筛. 相比于传统TiO₄物种作为催化活性中心(1-己烯的转化率<25%, 环氧化产物选择性>95%), 本文所制备的TS-1分子筛(Si/Ti=36.9)因其兼具TiO₄和TiO₆物种, 在1-己烯环氧化反应中表现出更好的催化性能(1-己烯的转化率33%, 环氧化产物选择性95%). 这是由于TiO₄物种不会导致开环反应的发生, 因此可以保证较高的环氧产物选择性, 而TiO₆物种经H₂O₂活化后, 可形成具有更高活性及更小位阻效应的催化中心, 极大提高了1-己烯转化率. 综上, 本文合成策略为构筑具有高活性钛物种及多级孔结构的钛硅分子筛提供了指导作用, 为调控硅铝酸盐及硅取代磷酸铝分子筛材料活性位点的含量和分布提供了新思路.

关键词: TS-1分子筛, 钛物种, L-氨基酸辅助, 1-己烯环氧化

Abstract:

Tailoring the Ti coordination states in titanosilicate zeolites to simultaneously improve feedstock conversion and maximize the target product selectivity remains a challenge in the pursuit of high-performance catalysts for selective oxidation reactions. Herein, we provide a facile strategy to synthesize hierarchical anatase-free TS-1 (MFI-type) zeolites with tetrahedrally coordinated (TiO₄) and octahedrally coordinated Ti species (TiO₆). The TiO₄ species provide high epoxide selectivity, while the TiO₆ species afford improved alkene conversion. This strategy is achieved by synergistically using an L-lysine-assisted approach and a two-step crystallization; the two-step crystallization approach prevents the formation of anatase TiO₂, while L-lysine stabilizes the TiO₆ species and ensures efficient incorporation of TiO₆ into the anatase-free TS-1 zeolites. Compared with their conventional counterparts, which only contain TiO₄ species, the as-prepared TS-1 zeolites (Si/Ti = 36.9) result in a higher 1-hexene conversion (33%), higher TON value (153), and comparable epoxide selectivity (95%). This synthetic strategy provides avenues to tailor the amount and distribution of Ti species in titanosilicate zeolites to achieve high catalytic performances in various processes.

Key words: TS-1 zeolites, Ti species, L-Lysine-assisted approach, 1-Hexene epoxidation

王煜瑶, 李莉, 白日升, 高士钦, 冯兆池, 张强, 于吉红. 氨基酸辅助合成高活性六配位钛物种的TS-1分子筛[J]. 催化学报, 2021, 42(12): 2189-2196.

Yuyao Wang, Li Li, Risheng Bai, Shiqin Gao, Zhaochi Feng, Qiang Zhang, Jihong Yu. Amino acid-assisted synthesis of TS-1 zeolites containing highly catalytically active TiO₆ species[J]. Chinese Journal of Catalysis, 2021, 42(12): 2189-2196.

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图/表 4

Fig. 1. XRD patterns (a), FTIR spectra (b), UV-vis spectra (c), and UV-Raman spectra excited at 266 nm (d) of the TS-1 zeolites.

Fig. 2. TEM images of TS-1-SL0-36 (a), TS-1-TL0-76 (b), TS-1-TL0.1-56 (c), and TS-1-TL0.2-36 (d).

Scheme 1. Proposed evolution of the TiO6 species stabilized by L-lysine in TS-1 zeolites.

Fig. 3. (a) Epoxidation reaction routes directed by TiO4 (closed sites) and TiO6 (open sites) species in the TS-1 zeolites, respectively; (b)1-Hexene conversion over the different TS-1 zeolites; (c) 1-Hexene conversion and product selectivity of the recycle test performed using TS-1-TL0.2-36.

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氨基酸辅助合成高活性六配位钛物种的TS-1分子筛

Amino acid-assisted synthesis of TS-1 zeolites containing highly catalytically active TiO₆ species

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氨基酸辅助合成高活性六配位钛物种的TS-1分子筛

Amino acid-assisted synthesis of TS-1 zeolites containing highly catalytically active TiO6 species

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Amino acid-assisted synthesis of TS-1 zeolites containing highly catalytically active TiO₆ species