Highly Efficient MIL-101(Fe) Catalyst for the Preparation of Nopol by the Prins Condensation of β-Pinene and Formaldehyde†

doi:10.7503/cjcu20180750

Abstract

Abstract:

Metal organic framework materials MIL-101(Fe) were prepared by hydrothermal synthesis method. All the catalysts were characterized by X-ray diffraction(XRD), Fourier transform infrared spectra(FTIR), thermogravimetric analysis(TG), scanning electron microscopy(SEM), transmission electron microscopy(TEM) and X-ray photoelectron spectroscopy(XPS). Those materials were applied for the catalytic condensation of β-pinene and formaldehyde, and achieved excellent catalytic result. The results indicated that the catalyst synthesis temperature, synthesis time, catalyst amount, solvent, reaction temperature and time have certain effects on the reaction results of condensation reaction. Under similar reaction conditions, MIL-101(Fe)-150-15 catalyst was found to be the most active in the Prins condensation of β-pinene and formaldehyde, for which 97.3% of conversion and 96.7% selectivity are achieved within 8 h at 90 ℃.

Key words: Metal organic framework material, MIL-101(Fe), β-Pinene, Acid catalysis, Nopol

CLC Number:

O643.3

TrendMD:

JING Run,LU Xinhuan,ZHANG Haifu,TAO Peipei,PAN Haijun,HU Ao,ZHOU Dan,XIA Qinghua. Highly Efficient MIL-101(Fe) Catalyst for the Preparation of Nopol by the Prins Condensation of β-Pinene and Formaldehyde^†[J]. Chem. J. Chinese Universities, 2019, 40(4): 755.

Figures/Tables 10

Scheme 1 Catalytic condensation of β-pinene and formaldehyde

Fig.1 XRD patterns of MIL-101(Fe) synthesized at different temperatures(A) and reaction time(B)

Fig.2 FTIR spectra of MIL-101(Fe) synthesized at different temperatures(A) and reaction time(B)

Fig.3 TG curve of MIL-101(Fe)-150-15 catalyst

Fig.4 SEM images of MIL-101(Fe)-130-15(A), MIL-101(Fe)-150-6(B), MIL-101(Fe)-150-15(C) and MIL-101(Fe)-170-15(D)

Fig.5 TEM images of MIL-101(Fe)-130-15(A), MIL-101(Fe)-150-6(B), MIL-101(Fe)-150-15(C) and MIL-101(Fe)-170-15(D)

Fig.6 XPS spectra of the MIL-101(Fe)-150-15 (A) Survey; (B) C1s; (C) O1s; (D) Fe2p.

Fig.7 Effects of reaction temperature(A) and reaction time(B) of MIL-101(Fe) on the Prins condensationReaction conditions: 50 mg catalyst; 2.0 mmol β-pinene; 4.0 mmol formaldehyde; 5 g toluene(solvent); 90 ℃; 8 h.

Fig.8 Effects of reaction conditions on the Prins condensation Reaction conditions: 50 mg MIL-101(Fe)-150-15; 2.0 mmol β-pinene; 4.0 mmol formaldehyde; 5 g solvent. a. Toluene; b. dioxane; c. xylene; d. DMF; e. ethylacetate; f. ethylbenzene.

Fig.9 Recycling tests(A), XRD patterns(B) and SEM images(C, D) of MIL-101(Fe)-150-15 catalystReaction conditions: 50 mg MIL-101(Fe)-150-15; 2.0 mmol β-pinene; 4.0 mmol formaldehyde; 5 g toluene(solvent); 90 ℃; 8 h. (C) Fresh; (D) reuse for 4 times.

References 23

[1]	Farha O. K., Yazaydin A. O., Eryazici I., Malliakas C. D., Hauser B. G., Kanatzidis M. G., Nguyen S. T., Snurr R. Q., Hupp J. T., Nature Chem.,2010, 2, 944—948
[2]	Furukawa H., Ko N., Go Y. B., Aratani N., Choi S. B., Choi E., Yazaydin A. O., Snurr R. Q., O’Keeffe M., Kim J., Yaghi O. M., Science,2010, 329, 424—428
[3]	O’Keeffe M., Chem. Soc.Rev., 2009, 38(5), 1215—1217
[4]	Eddaoudi M., Moler D. B., Li H., Chen B., Reineke T. M., O’Keeffe M., Yaghi O. M., Acc. Chem.Res.,2001, 34, 319—330
[5]	Zhang Y. M., Zhang J., Li X. F., Chu G., Tian M. M., Quan C. S., Chem. J. Chinese Universities,2016, 37(3), 573—580
	(张艳梅, 张静, 李晓芳, 储刚, 田苗苗, 权春善. 高等学校化学学报,2016, 37(3), 573—580)
[6]	Betard A., Fischer R. A., Chem.Rev.,2012, 112, 1055—1083
[7]	Yoon M., Srirambalaji R., Kim K., Chem.Rev.,2012, 112, 1196—1231
[8]	Horcajada P., Gref R., Baati T., Allan P. K., Maurin G., Couvreur P., Ferey G., Morris R. E., Sreer C., Chem.Rev.,2012, 112, 1232—1268
[9]	Kreno L. E., Leong K., Farha O. K., Allendorf M., Duyne R. P. V., Hupp J. T., Chem.Rev.,2012, 112, 1105—1125
[10]	Allendorf M. D., Bauer C. A., Bhakta R. K., Houk R. J. T., Chem. Soc.Rev.,2009, 38, 1330—1352
[11]	Cui Y., Yue Y., Qian G., Chen B., Chem.Rev.,2012, 112(2), 1126—1162
[12]	Rocha J., Carlos L. D., Paz F. A. A., Ananias D., Chem. Soc.Rev.,2011, 40, 926—940
[13]	Horcajada P., Serre C., Maurin G., Ramsahye N. A., Balas F., Vallet-Regi M., Sebban M., Taulelle F., Férey G., J. Am. Chem.Soc.,2008, 130, 6774—6780
[14]	Feng X. W., Chen H., Jiang F., J. Colloid Interf.Sci.,2017, 494, 32—37
[15]	Lee J. Y., Farha O. K., Roberts J., Scheidt K. A., Nguyen S. T., Hupp J. T., Chem. Soc.Rev.,2009, 38, 1450—1459
[16]	Hoskins B. F., Robson R., J. Am. Chem.Soc.,1990, 112, 1546—1554
[17]	Férey G., Mellot-Draznieks C., Serre C., Millange F., Dutour J., Surble S., Margiolaki I., Science, 2005, 309, 2040—2042
[18]	Wang K., Xu L., Chen H. Z., Qiao H. Y., Chen C., Zhang N., Chem. J. Chinese Universities,2016, 37(4), 723—727
	(王凯, 徐力, 陈恒泽, 乔慧颖, 陈超, 张宁. 高等学校化学学报, 2016, 37(4), 723—727)
[19]	Zalomaeva O. V., Chibiryaev A. M., Kovalenko K. A., Kholdeeva O. A., Balzhinimaev B. S., Fedin V. P., J.Catal.,2013, 298, 179—185
[20]	Jadhav S. V., Jinka K. M., Bajaj H. C., Appl. Catal. A:Gen.,2010,390, 158—165
[21]	Do D. M., Jaenicke S., Chuah G. K., Catal. Sci.Technol.,2012, 2, 1417—1424
[22]	Loiseau T., Serre C., Huguenard C., Fink G., Taulelle F., Henry M., Bataille T., Férey G., Chem. Eur.J.,2004, 10, 1373—1382
[23]	Vu T. A., Le G. H., Dao C. D., Dang L. Q., Nguyen K. T., Dang P. T., Tran H. T. K., Duong Q. T., Nguyen T. V., Lee G. D., RSC Adv.,2014, 4, 41185—41194