Solvothermal synthesis of Co-substituted phosphomolybdate acid encapsulated in the UiO-66 framework for catalytic application in olefin epoxidation

doi:10.1016/S1872-2067(20)63665-8

Abstract

Abstract:

Hybrid composites of phosphomolybdic acid@UiO-66 (PMo₁₂@UiO-66) and Co-substituted phosphomolybdic acid@UiO-66 (PMo₁₁Co@UiO-66) were synthesized using the direct solvothermal method. A variety of characterization results demonstrated that phosphomolybdic acid (PMo₁₂) or Co-substituted phosphomolybdate acid (PMo₁₁Co) clusters are uniformly dispersed in the cages of Zr-based metal-organic UiO-66 frameworks. The catalytic properties of these hybrid composites were investigated by applying the epoxidation of olefins with tert-butyl hydroperoxide as the oxidant. Compared to PMo₁₂@UiO-66, PMo₁₁Co@UiO-66 showed a much higher catalytic activity and was simply recovered by filtration and reused for at least ten runs without significant loss of catalytic activity. Particularly, PMo₁₁Co@UiO-66 can efficiently convert cyclic olefins like limonenes to epoxides, and its selectivity to 1,2-limonene oxide reached 91% in the presence of a radical inhibitor such as hydroquinone. The excellent catalytic activity and stability of the hybrid composite PMo11Co@UiO-66 are mainly attributed to the uniform distribution of highly active PMo11Co units within the smaller cages of UiO-66, to the suitable surface polarity of the hybrid composite for facilitating the access of reagents and solvent, and to the strong interface-interactions between the polyoxometalate and the UiO-66 framework.

Key words: Polyoxometalate, Metal-organic frameworks, Olefins, Epoxidation, Solvothermal synthesis

Dianwen Hu, Xiaojing Song, Shujie Wu, Xiaotong Yang, Hao Zhang, Xinyu Chang, Mingjun Jia. Solvothermal synthesis of Co-substituted phosphomolybdate acid encapsulated in the UiO-66 framework for catalytic application in olefin epoxidation[J]. Chinese Journal of Catalysis, 2021, 42(2): 356-366.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63665-8

https://www.cjcatal.com/EN/Y2021/V42/I2/356

Figures/Tables 16

Table 1 Textural parameters derived from N2 adsorption-desorption profiles as well as element compositions determined by ICP-OES analyses of various materials.

Sample	BET surface area (m²·g^-1)	Pore volume (cm³·g^-1)	Pore diameter (nm)	POM loading (mmol·g^-1/wt%)	Mo loading (mmol·g^-1/wt%)	Co loading (mmol·g^-1/wt%)
UiO-66	1202	0.58	1.9	—	—	—
PMo₁₂@UiO-66	994	0.53	2.1	(0.040/7.3)	(0.480/4.6)	—
PMo₁₁Co@UiO-66	991	0.51	2.0	(0.038/6.7)	(0.418/4.0)	(0.038 /0.2)
PMo₁₁Co/UiO-66-imp	956	0.47	1.9	(0.037/6.6)	(0.407/3.9)	(0.037 / 0.2)

Fig. 1. XRD patterns of simulated UiO-66, UiO-66, and POM@UiO-66 composites.

Fig. 2. SEM images of UiO-66 (a), PMo12@UiO-66 (b), and PMo11Co@UiO-66 (c); (d,e) TEM images of PMo11Co@UiO-66; (f) HAADF-STEM image of PMo11Co@UiO-66; (g-i) EDS mapping images of PMo11Co@UiO-66.

Fig. 3. TG curves of UiO-66, PMo12@UiO-66, and PMo11Co@UiO-66.

Fig. 4. (A) N2 adsorption-desorption isotherms of UiO-66, PMo12@UiO-66, and PMo11Co@UiO-66 composites; (B) Pore size distribution curves of UiO-66, PMo12@UiO-66, and PMo11Co@UiO-66 composites.

Fig. 5. FT-IR spectra of PMo12, PMo11Co, UiO-66, and POM@UiO-66 composites.

Fig. 6. (A) DR-UV-vis spectra of PMo12 and PMo11Co; (B) DR-UV-vis spectra of UiO-66 and POM@UiO-66 composites.

Fig. 7. (A) XPS profiles for the binding energies of Mo 3d in PMo12, PMo11Co, PMo11Co@UiO-66, and reused PMo11Co@UiO-66; (B) XPS profiles for the binding energies of Co 2p in PMo11Co, PMo11Co@UiO-66, and reused PMo11Co@UiO-66.

Table 2 Cyclooctene epoxidation performance of various catalyst samples a.

Entry	Catalyst	Amount of catalyst (mg)	Time (h)	Conversion (%)	TOF^b(h^-1)	Related work
1	Blank	—	6	3	—	This work
2	UiO-66	10	6	3	—	This work
3	PMo₁₂@UiO-66	10	6	32	11	This work
4	PMo₁₁Co@UiO-66	10	6	52	19 ^c	This work
5	PMo₁₁Co/UiO-66-imp	10	6	40	15 ^c	This work
6	PMo₁₂@COF-300 ^f	10	3	63	44	[40]
7	Mo(CO)₃-L@UiO-66 ^d	100	4.5	98	19	[46]
8	PMo₁₂@meso-organosilicates ^e	100	6	58	4	[47]

Fig. 8. Leaching (A) and recycling (B) experiments of PMo11Co@UiO-66. Reaction conditions: cyclooctene 5.0 mmol, t-BuOOH 5.0 mmol, PMo11Co@UiO-66 50 mg, solvent 15 ml, 334 K, 6 h. All epoxide selectivity was greater than 99%.

Fig. 9. Solvent effect on cyclooctene epoxidation. Reaction conditions: cyclooctene 1.0 mmol, t-BuOOH 1.0 mmol, PMo11Co@UiO-66 10 mg, solvent 3 ml, 334 K, 6 h. Selectivity for the epoxide is greater than 99%.

Table 3 Epoxidation of olefins catalyzed by PMo11Co@UiO-66 a.

Entry	Conversion^c (%)	Selectivity^c(%)	TOF (h^-1)
1^b	55	69^d	10
2	68	>99	12
3	61	71^d	11
4	63	74^d	12
5	16	>99	3
6	12	>99	2
7	42	69^d	8

Fig. 10. Conversion and selectivity during selective limonene oxidation. Reaction conditions: limonene 10 mmol, t-BuOOH 20 mmol, catalyst 100 mg, chloroform 30 mL, reaction temperature 334 K.

Fig. 11. Scheme 1. Typical synthesis of POM@UiO-66 composites.

Fig. 12. Scheme 2. Main products of selective limonene oxidation.

Fig. 13. Scheme 3. Proposed oxygen activation mechanism of t-BuOOH.

References

[1]	M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. O’Keeffe, O. M. Yaghi, Science, 2002,295, 469-472.
[2]	J. W. Yoon, S. H. Jhung, Y. K. Hwang, S. M. Humphrey, P. T. Wood, J. S. Chang, Adv. Mater., 2007,19, 1830-1834.
[3]	J. R. Li, R. J. Kuppler, H. C. Zhou, Chem. Soc. Rev., 2009,38, 1477-1504.
[4]	R. Matsuda, R. Kitaura, S. Kitagawa, Y. Kubota, R. V. Belosludov, T. C. Kobayashi, H. Sakamoto, T. Chiba, M. Takata, Y. Kawazoe, Y. Mita, Nature, 2005,436, 238-241.
[5]	G. J. Halder, C. J. Kepert, B. Moubaraki, K. S. Murray, J. D. Cashion, Science, 2002,298, 1762-1765.
[6]	O. R. Evans, W. Lin, Acc. Chem. Res., 2002,35, 511-522.
[7]	J. Liu, L. Chen, H. Cui, J. Zhang, L. Zhang, C. Y. Su, Chem. Soc. Rev., 2014,43, 6011-6061.
[8]	L. Jiao, Y. Wang, H. L. Jiang, Q. Xu, Adv. Mater., 2018,30, e1703663.
[9]	S. T. Gao, W. Liu, C. Feng, N. Z. Shang, C. Wang, Catal. Sci. Technol., 2016,6, 869-874.
[10]	L. Shen, W. Wu, R. Liang, R. Lin, L. Wu, Nanoscale, 2013,5, 9374-9382.
[11]	C. S. Hinde, W. R. Webb, B. K. Chew, H. R. Tan, W. H. Zhang, T. S. Hor, R. Raja, Chem. Commun., 2016,52, 6557-6560.
[12]	J. C. Wang, Y. H. Hu, G. J. Chen, Y. B. Dong, Chem. Commun., 2016,52, 13116-13119.
[13]	M. Kaposi, M. Cokoja, C. H. Hutterer, S. A. Hauser, T. Kaposi, F. Klappenberger, A. Pothig, J. V. Barth, W. A. Herrmann, F. E. Kuhn, Dalton Trans., 2015,44, 15976-15983.
[14]	L. Chen, R. Luque, Y. Li, Dalton Trans., 2018,47, 3663-3668.
[15]	F. Zhang, S. Zheng, Q. Xiao, Y. Zhong, W. Zhu, A. Lin, M. Samy El Shall, Green Chem., 2016,18, 2900-2908.
[16]	M. W. Logan, Y. A. Lau, Y. Zheng, E. A. Hall, M. A. Hettinger, R. P. Marks, M. L. Hosler, F. M. Rossi, Y. Yuan, F. J. Uribe-Romo, Catal. Sci. Technol., 2016,6, 5647-5655.
[17]	R. Insyani, D. Verma, S. M. Kim, J. Kim, Green Chem., 2017,19, 2482-2490.
[18]	J. Chen, K. Li, L. Chen, R. Liu, X. Huang, D. Ye, Green Chem., 2014,16, 2490-2499.
[19]	H. G. T. Nguyen, L Mao, A W. Peters, C O. Audu, Z J. Brown, O K. Farha, J T. Hupp, S T. Nguyen, Catal. Sci. Technol., 2015,5, 4444-4451.
[20]	A. H. Valekar, K. H. Cho, S. K. Chitale, D. Y. Hong, G. Y. Cha, U. H. Lee, D. W. Hwang, C. Serre, J. S. Chang, Y. K. Hwang, Green Chem., 2016,18, 4542-4552.
[21]	M. Lammert, M. T. Wharmby, S. Smolders, B. Bueken, A. Lieb, K. A. Lomachenko, D. D. Vos, N. Stock, Chem. Commun., 2015,51, 12578-12581.
[22]	F. Nouar, M. I. Breeze, B. C. Campo, A. Vimont, G. Clet, M. Daturi, T. Devic, R. I. Walton, C. Serre, Chem. Commun., 2015,51, 14458-14461.
[23]	A. Dhakshinamoorthy, A. Santiago-Portillo, A. M. Asiri, H. Garcia, ChemCatChem, 2019,11, 899-923.
[24]	W. Xie, F. Wan, Chem. Eng. J., 2019,365, 40-50.
[25]	X. L. Yang, L. M. Qiao, W. L. Dai, Microporous Mesoporous Mater., 2015,211, 73-81.
[26]	X. M. Zhang, Z. Zhang, B. Zhang, X. Yang, X. Chang, Z. Zhou, D. H. Wang, M. H. Zhang, X. H. Bu, Appl. Catal. B, 2019,256, 117804.
[27]	X. Chang, X. F. Yang, Y. Qiao, S. Wang, M. H. Zhang, J. Xu, D. H. Wang, X. H. Bu, Small, 2020, DOI: 10.1002/smll.201906432, 1906432.
[28]	C. T. Buru, P. Li, B. L. Mehdi, A. Dohnalkova, A. E. P. Prats, N D. Browning, K W. Chapman, J T. Hupp, O K. Farha, Chem. Mater., 2017,29, 5174-5181.
[29]	W. Salomon, C. Roch-Marchal, P. Mialane, P. Rouschmeyer, C. Serre, M. Haouas, F. Taulelle, S. Yang, L. Ruhlmann, A. Dolbecq, Chem. Commun., 2015,51, 2972-2975.
[30]	G. Férey, C. Mellot-Draznieks, C. Serre, F. Millange, J. Dutour, S. Surblé, I. Margiolaki, Science, 2005,309, 2040-2042.
[31]	W. Salomon, F. J. Yazigi, C. Roch-Marchal, P. Mialane, P. Horcajada, C. Serre, M. Haouas, F. Taulelle, A. Dolbecq, Dalton Trans., 2014,43, 12698-12705.
[32]	N. V. Maksimchuk, O. A. Kholdeeva, K. A. Kovalenko, V. P. Fedin, Isr. J. Chem., 2011,51, 281-289.
[33]	X. Song, D. Hu, X. Yang, H. Zhang, W. Zhang, J. Li, M. Jia, J. Yu, ACS Sustain. Chem. Eng., 2019,7, 3624-3631.
[34]	X. Song, W. Zhu, K. Li, J. Wang, H. Niu, H. Gao, W. Gao, W. Zhang, J. Yu, M. Jia, Catal. Today, 2016,259, 59-65.
[35]	A. Schaate, P. Roy, A. Godt, J. Lippke, F. Waltz, M. Wiebcke, P. Behrens, Chem. Eur. J., 2011,17, 6643-6651.
[36]	B. Tu, Q. Pang, H. Xu, X. Li, Y. Wang, Z. Ma, L. Weng, Q. Li, J. Am. Chem. Soc., 2017,139, 7998-8007.
[37]	J. She, Z. Fu, J. Li, B. Zeng, S. Tang, W. Wu, H. Zhao, D. Yin, S. R. Kirk, Appl. Catal. B, 2016,182, 392-404.
[38]	N. Afzali, R. Kardanpour, F. Zadehahmadi, S. Tangestaninejad, M. Moghadam, V. Mirkhani, A. Mechler, I. M. Baltork, M. Bahadori, Appl. Organomet. Chem., 2019,33, e5225.
[39]	X. Song, Y. Yan, Y. Wang, D. Hu, L. Xiao, J. Yu, W. Zhang, M. Jia, Dalton Trans., 2017,46, 16655-16662.
[40]	W. Gao, X. Sun, H. Niu, X. Song, K. Li, H. Gao, W. Zhang, J. Yu, M. Jia, Microporous Mesoporous Mater., 2015,213, 59-67.
[41]	X. Song, W. Zhu, Y. Yan, H. Gao, W. Gao, W. Zhang, M. Jia, J. Mol. Catal. A, 2016,413, 32-39.
[42]	X. Song, W. Zhu, Y. Yan, H. Gao, W. Gao, W. Zhang, M. Jia, Microporous Mesoporous Mater., 2017,242, 9-17.
[43]	C. Qin, A. Fan, D. Ren, C. Luan, J. Yang, Y. Liu, X. Zhang, X. Dai, M. Wang, Electrochim. Acta, 2019,323, 134756.
[44]	M. C. Biesinger, B. P. Payne, A. P. Grosvenor, L. W. M. Lau, A R. Gerson, R S. C. Smart, Appl. Surf. Sci., 2011,257, 2717-2730.
[45]	Q. Zhang, J. Zhang, H. Yang, Y. Dong, Y. Liu, L. Yang, D. Wei, W. Wang, L. Bai, H. Chen, Catal. Sci. Technol., 2019,9, 2915-2922.
[46]	N. Afzali, S. Tangestaninejad, M. Moghadam, V. Mirkhani, A. Mechler, I. Mohammadpoor-Baltork, R. Kardanpour, F. Zadehahmadi, Appl. Organomet. Chem., 2018,32, e3958.
[47]	J. Wang, Y. Zou, Y. Sun, M. Hemgesberg, D. Schaffner, H. Gao, X. Song, W. Zhang, M. Jia, W. R. Thiel, Chin. J. Catal., 2014,35, 532-539.
[48]	A. Gallo, C. Tiozzo, R. PsaroF, F. Carniato, M. Guidotti, J. Catal., 2013,298, 77-83.
[49]	S. Lwin, Y. Li, A. I. Frenkel, I. E. Wachs, ACS Catal., 2016,6, 3061-3071.
[50]	X. Carrier, E. Marceau, H. Carabineiro, V. Rodriguez-Gonzalez, M. Che, Phys. Chem. Chem. Phys., 2009,11, 7527-7539.
[51]	C. Bisio, A. Gallo, R. Psaro, C. Tiozzo, M. Guidotti, F. Carniato, Appl. Catal. A, 2019,581, 133-142.
[52]	J. Hu, K. Li, W. Li, F. Ma, Y. Guo, Appl. Catal. A, 2009,364, 211-220.
[53]	J. Liu, T. Chen, P. Jian, L. Wang, Chin. J. Catal., 2018,39, 1942-1950
[54]	J. Liu, R. Meng, J. Li, P. Jian, L. Wang, R. Jian, Appl. Catal. B, 2019,254, 214-222.
[55]	J. Hafizovic Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti, S. Bordiga, K. P. Lillerud, J. Am. Chem. Soc., 2008,130, 13850-13851.
[56]	C. Ci, H. Liu, L. Yan, Z. Su, ChemistryOpen, 2016,5, 470-476.
[57]	M. Bagherzadeh, L. Tahsini, R. Latifi, L. K. Woo, Inorg. Chim. Acta, 2009,362, 3698-3702.
[58]	M. Bagherzadeh, M. Zare, V. Amani, A. Ellern, L. Keith Woo, Polyhedron, 2013,53, 223-229.
[59]	F. Payami, A. Bezaatpour, H. Eskandari, Appl. Organomet. Chem., 2018,32, e3986.
[60]	P. Jiménez-Lozano, I. Y. Skobelev, O. A. Kholdeeva, J. M. Poblet, J. J. Carbó, Inorg. Chem., 2016,55, 6080-6084.
[61]	N. V. Maksimchuk, G. M. Maksimov, V. Y. Evtushok, I. D. Ivanchikova, Y. A. Chesalov, R. I. Maksimovskaya, O. A. Kholdeeva, A. Solé-Daura, J. M. Poblet, J. J. Carbó, ACS Catal., 2018,8, 9722-9737.