双功能TiSn-Beta分子筛限域的串联Lewis酸催化烯烃生成1,2-二醇

doi:10.1016/S1872-2067(20)63734-2

催化学报 ›› 2021, Vol. 42 ›› Issue (7): 1176-1184.DOI: 10.1016/S1872-2067(20)63734-2

双功能TiSn-Beta分子筛限域的串联Lewis酸催化烯烃生成1,2-二醇

雷琦锋^a, 王畅^a, 戴卫理^a^,^*(), 武光军^a, 关乃佳^a^,^b, Michael Hunger^c, 李兰冬^a^,^b

^a南开大学材料科学与工程学院, 国家新材料研究院, 天津300350, 中国
^b南开大学先进能源材料化学教育部重点实验室, 化学化工协同创新中心, 天津300071, 中国
^c斯图加特大学化学技术研究所, 斯图加特70550, 德国

收稿日期:2020-09-22 接受日期:2020-11-02 出版日期:2021-07-18 发布日期:2020-12-10
通讯作者: 戴卫理
基金资助:
天津市自然科学基金(18JCJQJC47400);天津市自然科学基金(18JCZDJC37400);中央高校基本科研业务经费

Tandem Lewis acid catalysis for the conversion of alkenes to 1,2-diols in the confined space of bifunctional TiSn-Beta zeolite

Qifeng Lei^a, Chang Wang^a, Weili Dai^a^,^*(), Guangjun Wu^a, Naijia Guan^a^,^b, Michael Hunger^c, Landong Li^a^,^b

^aSchool of Materials Science and Engineering & National Institute for Advanced Materials, Nankai University, Tianjin 300350, China
^bKey Laboratory of Advanced Energy Materials Chemistry of the Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin 300071, China
^cInstitute of Chemical Technology, University of Stuttgart, Stuttgart 70550, Germany

Received:2020-09-22 Accepted:2020-11-02 Online:2021-07-18 Published:2020-12-10
Contact: Weili Dai
About author:^* Tel/Fax: +86-22-85358536; E-mail: weilidai@nankai.edu.cn
Supported by:
Municipal Natural Science Foundation of Tianjin(18JCJQJC47400);Municipal Natural Science Foundation of Tianjin(18JCZDJC37400);Fundamental Research Funds for the Central Universities

摘要/Abstract

摘要：

1,2-二醇主要由环氧化合物水合产生、广泛用于防冻剂, 聚酯树脂和医药等化学品中间体的生产. 研究表明, 具有Lewis酸性的含锡沸石分子筛在环氧化物的水合反应中表现出优异的催化性能. 环氧化合物是众所周知的碳亲电体之一, 主要由烯烃环氧化生成. 含Ti(IV)沸石, 如Ti-Beta和TS-1, 是烯烃环氧化反应的高效催化剂. 串联催化可以将多步反应整合为一次反应, 无需分离中间体, 有效缩短合成路线, 提高生产效率. 因此, 双功能Ti和Sn分子筛有望应用于烯烃制二醇的串联催化反应中, 即烯烃在Ti活性位点上发生环氧化反应, 随后在Sn位点上发生水合反应, 进而串联一步生成1,2-二醇. 在沸石分子筛中产生孤立的多功能活性位点是将多步反应整合成串联催化反应的一种有吸引力的设计策略.
本文通过简单且可规模制备的后合成路线构建了双功能TiSn-Beta分子筛, 并用于烯烃串联催化制1,2-二醇反应. 一方面, 该反应中的过氧化氢溶液既能提供氧化剂(如H₂O₂)用于烯烃环氧化反应, 又能提供环氧化合物水合反应的亲核试剂(如H₂O); 同时TiSn-Beta作为一种高效双功能催化剂, 孤立的Ti和Sn活性中心可以有效地将烯烃环氧化反应和环氧化物水合反应串联在沸石微反应器中, 实现烯烃一步转化为1,2-二醇. 另一方面, 沸石的限域效应较好地保证了烯烃环氧化和环氧化物水合的高串联速率和目标产物的高选择性, 在最优的反应条件下, 1,2-二醇选择性高达90%以上, 收率接近70%. 本文结果表明沸石分子筛是构筑多功能孤立活性位点的理想载体, 为其他串联反应催化剂的设计提供了良好的借鉴.

关键词: 串联催化剂, 限域效应, 分子筛, 烯烃环氧化, 环氧化合物水合

Abstract:

The generation of multifunctional isolated active sites in zeolite supports is an attractive method for integrating multistep sequential reactions into a single-pass tandem catalytic reaction. In this study, bifunctional TiSn-Beta zeolite was prepared by a simple and scalable post-synthesis approach, and it was utilized as an efficient heterogeneous catalyst for the tandem conversion of alkenes to 1,2-diols. The isolated Ti and Sn Lewis acid sites within the TiSn-Beta zeolite can efficiently integrate alkene epoxidation and epoxide hydration in tandem in a zeolite microreactor to achieve one-step conversion of alkenes to 1,2-diols with a high selectivity of >90%. Zeolite confinement effects result in high tandem rates of alkene epoxidation and epoxide hydration as well as high selectivity toward the desired product. Further, the novel method demonstrated herein can be employed to other tandem catalytic reactions for sustainable chemical production.

Key words: Tandem catalysis, Confinement effect, Zeolite, Alkene epoxidation, Epoxide hydration

雷琦锋, 王畅, 戴卫理, 武光军, 关乃佳, Michael Hunger, 李兰冬. 双功能TiSn-Beta分子筛限域的串联Lewis酸催化烯烃生成1,2-二醇[J]. 催化学报, 2021, 42(7): 1176-1184.

Qifeng Lei, Chang Wang, Weili Dai, Guangjun Wu, Naijia Guan, Michael Hunger, Landong Li. Tandem Lewis acid catalysis for the conversion of alkenes to 1,2-diols in the confined space of bifunctional TiSn-Beta zeolite[J]. Chinese Journal of Catalysis, 2021, 42(7): 1176-1184.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63734-2

https://www.cjcatal.com/CN/Y2021/V42/I7/1176

图/表 9

Fig. 1. Routes for the conversion of alkenes to 1,2-diols. Route a: indirect route including two processes: alkene epoxidation and epoxide hydration. Route b: tandem catalytic route of this study.

Table 1 Physicochemical properties of the samples under study.

Samples	Si/Al ratio ^a	Ti loading ^a (wt%)	Sn loading ^a (wt%)	Surface area ^b (m²/g)	Pore volume ^c (cm³/g)
H-Beta	13.5	—	—	590	0.204
Si-Beta	>1800	—	—	620	0.210
Ti-Beta	>1800	4.8	—	598	0.199
Sn-/Beta	>1800	—	4.9	605	0.201
TiSn-Beta	>1800	4.6	4.7	588	0.192
TiSn-Beta ^d	>1800	4.5	4.7	580	0.191

Fig. 2. (a) XRD patterns of the samples; (b) DRIFT spectra of the samples in the hydroxyl stretching vibration region.

Fig. 3. 29Si MAS NMR spectra of the as-prepared samples under study.

Fig. 4. (a) HAADF-STEM images with the corresponding element mapping of TiSn-Beta zeolite; Ti 2p (b) and Sn 3d (c) XPS of Ti- and Sn- containing samples.

Fig. 5. (a) UV-vis spectra of the dehydrated samples; (b) 119Sn MAS NMR spectra of the Sn-Beta and TiSn-Beta samples before and after hydration; (c) 1H MAS NMR spectra of the dehydrated samples before (top) and after (middle) ammonia loading. The difference spectra (bottom) were obtained by subtracting the top spectra from the middle spectra; (d) 31P MAS NMR spectra of TMPO-loaded samples.

Fig. 6. (a) Product yields over the different catalysts (TiSn-Beta: Ti and Sn were co-introduced; Ti-Sn-Beta: Ti was first introduced followed by Sn; Sn-Ti-Beta: Sn was first introduced followed by Ti). (b) Product yields during cyclohexene conversion over TiSn-Beta zeolite with different Ti and Sn weight loadings (2.5%:7.5%, 5%:5%, and 7.5%:7.5%). (c) Effect of reaction temperature on cyclohexene conversion and 1,2-cyclohexanediol selectivity catalyzed by TiSn-Beta zeolite. (d) Cyclohexene conversion and diol selectivity during cyclohexene conversion over TiSn-Beta zeolite, plotted as a function of time-on-stream. Reaction conditions: 5 mmol cyclohexene; 2.5 mL of MeCN ((a) and (b)), MeCOMe ((c) and (d)); 5 mmol H2O2; 0.1 g of catalyst; temperature 333 K ((a), (b), and (d)), 313-353K (c); and time 2 h ((a), (b), and (c)), 0-6 h ((d)).

Fig. 7. Recycling tests of cyclohexene conversion catalyzed by TiSn-Beta zeolite without (a) and with calcination (b). Reaction conditions: 5 mmol cyclohexene, 2.5 mL of MeCOMe, 5 mmol H2O2, 0.1 g of catalyst, temperature 333 K, and time 2 h. XRD patterns (c) and UV-vis spectra (d) of the fresh and spent TiSn-Beta catalyst after 4 cycles.

Table 2 Catalytic performance of TiSn-Beta for the conversion of various alkenes.

Substrate	Conversion (%)	Selectivity (%)
Substrate	Conversion (%)	Epoxide	1,2-Diol	Others
	74.6	0.4	93.4	6.2
	57.5	1.2	78.6	20.2
	79.8	3.7	70.2	26.1
	46.1	95.8	4.2	0
	71.4	91.5	7.4	1.1
	6.7	32.6	22.1	45.3

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双功能TiSn-Beta分子筛限域的串联Lewis酸催化烯烃生成1,2-二醇

Tandem Lewis acid catalysis for the conversion of alkenes to 1,2-diols in the confined space of bifunctional TiSn-Beta zeolite

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