Direct hydrothermal synthesis of Mo-containing MFI zeolites using Mo-EDTA complex and their catalytic application in cyclohexene epoxidation

doi:10.1016/S1872-2067(21)63826-3

Abstract

Abstract:

A series of Mo-containing MFI zeolites with different Mo loadings (Mo-MFI-n, n represent the initial Si/Mo molar ratio) was hydrothermally synthesized by using tetrapropylammonium hydroxide as the template and Mo-EDTA complex as the Mo source. Various characterization results demonstrated that the use of the Mo-EDTA complex is beneficial for the incorporation of more Mo species into the MFI-type zeolites. The special complexing capability of EDTA^2- plays a critical role in adjusting the release rate of the Mo species to combine with the Si tetrahedron species during the zeolite growth process, thus leading to a uniform distribution of Mo in the MFI framework. In addition, a small portion of extra-framework Mo clusters may be distributed inside the channels or near the pore window of the zeolites. The catalytic properties of these Mo-containing MFI zeolites were evaluated for the epoxidation of cyclohexene with H₂O₂ as the oxidant. The composition-optimized catalyst, Mo-MFI-50, efficiently converted cyclohexene to the corresponding epoxide with a relatively high conversion (93%) and epoxide selectivity (82%) at 75 °C after 9 h of reaction. Moreover, the resultant Mo-containing MFI catalyst exhibited excellent structural stability and recoverability and was easily recycled by simple filtration without the need for calcination treatment.

Key words: MFI zeolite, Molybdenum catalyst, Ethylenediamine tetraacetic sodium, Cyclohexene, Epoxidation

Haoyang Zhang, Lifen Xu, Xinyu Chang, Songsong Miao, Yuting Sun, Mingjun Jia. Direct hydrothermal synthesis of Mo-containing MFI zeolites using Mo-EDTA complex and their catalytic application in cyclohexene epoxidation[J]. Chinese Journal of Catalysis, 2021, 42(12): 2265-2274.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63826-3

https://www.cjcatal.com/EN/Y2021/V42/I12/2265

Figures/Tables 11

Table 1 Mo contents and texture parameters of various Mo-MFI zeolites.

Sample	Mo content ^a (wt%)	A_BET^b (m²g^-1)	V_micro^c (m³g^-1)	RC ^d (%)
Mo-MFI-200	0.10	345	0.096	88
Mo-MFI-100	0.15	346	0.099	86
Mo-MFI-67	0.21	371	0.096	88
Mo-MFI-50	0.24	376	0.087	85
Mo-MFI-50-ref	0.07	345	0.120	100
Mo-MFI-40	0.32	325	0.116	70
Mo/S-1-ref	0.80	177	0.042	—
Spent Mo-MFI-50 ^e	0.24	365	0.096	—

Fig. 1. XRD patterns of various Mo-MFI zeolites.

Fig. 2. N2 adsorption-desorption isotherms of various Mo-MFI zeolites.

Fig. 3. SEM image of Mo-MFI-50 (a) and corresponding EDS elemental analysis (b) and mapping images: O (c), Si (d), Mo (e).

Fig. 4. TEM (a) and HRTEM (b) images of Mo-MFI-50.

Fig. 5. FT-IR spectra (a) and DRUV-vis spectra (b) of various Mo-MFI samples.

Fig. 6. Raman spectra of various Mo-containing MFI samples.

Table 2 Catalytic performance of various Mo-containing MFI catalysts in the epoxidation of cyclohexene with H2O2 as the oxidant.

Catalyst	Conversion (%)	Selectivity (mol%)				TOF^a
Catalyst	Conversion (%)	epoxide	CyH-ol	CyH-one	diol	(h^-1)
Mo-MFI-200	36.5	84.4	4.3	3.9	7.4	934
Mo-MFI-100	39.9	89.4	3.6	3.3	3.7	681
Mo-MFI-67	41.1	89.3	3.4	4.2	3.1	501
Mo-MFI-50	71.8	84.8	4.9	5.2	5.1	766
Mo-MFI-50-ref	13.5	85.1	4.6	6.0	4.3	494
Mo-MFI-40	42.9	90.2	3.2	4.2	2.4	343
Mo/S-1-ref	11.2	13.9	25.4	35.2	25.5	35.8

Fig. 7. Time-dependent profiles of the catalytic performance of Mo-MFI-50 (a) and Mo-MFI-50-ref (b). Reaction conditions: 20 mmol cyclohexene, 40 mmol H2O2 (30 wt%), 0.3 g catalyst, 5 mL acetonitrile, 75 °C.

Fig. 8. Effect of the reaction temperature on the catalytic performance of Mo-MFI-50. Reaction conditions: 20 mmol cyclohexene, 40 mmol H2O2 (30 wt%), 0.3 g catalyst, 5 mL acetonitrile, and 9 h.

Fig. 9. Recyclability of Mo-MFI-50 for cyclohexene epoxidation. Reaction conditions: 20 mmol cyclohexene, 40 mmol H2O2 (30 wt%), 0.3 g catalyst, 5 mL acetonitrile, 75 °C, and 9 h.

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