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

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

Abstract

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

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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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63734-2

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

Figures/Tables 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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