Improved catalytic performance and stability of defected UiO-66–SO3H in the esterification reaction of cyclohexene with cyclohexanecarboxylic acid
Source abstract
Abstract
The preparation of cyclohexanol by indirect hydration of cyclohexene is divided into two steps. Firstly, cyclohexene is esterified with formic acid, and then the resulted cyclohexyl formate is hydrolyzed to obtain cyclohexanol and formic acid. The key step in this process is the acid-catalyzed esterification reaction. Because formic acid had a great destructive effect on the structure of metal organic frameworks catalysts, cyclohexanecarboxylic acid was selected to replace formic acid in the esterification of cyclohexene in this work. Cyclohexanecarboxylic acid is relatively weak in polarity and acidity, and the molecular size of which is relatively large, therefore, a catalyst with abundant acid content and suitable pore size distribution needs to be constructed. The sulfonic acid functionalized UiO-66–SO3Hdef material containing lattice defects was prepared using acetic acid as the modulator, UiO-66 and UiO-66–SO3H without lattice defects were also prepared for comparison, and the samples were characterized by various methods. The acid content and acid strength of the UiO-66–SO3Hdef material were significantly increased, a greater proportion of mesoporous structure was obtained from the resulting defects sites. Compared to UiO-66 and UiO-66–SO3H, which were inactive in the esterification reaction of cyclohexene and cyclohexanecarboxylic acid, the UiO-66–SO3Hdef material had a significant improvement in its catalytic performance. The conversion rate of cyclohexene was up to 50.54%, and the selectivity of cyclohexyl carboxylate was 86.56%. After five times of reuse, the catalytic performance had no significant decrease, and the structure of the recovered catalyst remained unchanged.
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Research context
OpenAlex topics: Metal-Organic Frameworks: Synthesis and Applications · Polyoxometalates: Synthesis and Applications · Carbon dioxide utilization in catalysis
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (28)
Show source-provided references
1. G. Neri et al., Hydrogenation of phenol to cyclohexanone over palladium and alkali-doped palladium catalysts. Appl. Catal. A 110(1), 49–59 (1994)10.1016/0926-860X(94)80104-5 ↗
2. L.M.D.R. Martins et al., Efficient cyclohexane oxidation with hydrogen peroxide catalysed by a C-scorpionate iron(II) complex immobilized on desilicated MOR zeolite. Appl. Catal. A 464–465, 43–50 (2013)10.1016/j.apcata.2013.05.022 ↗
3. Y. Hong, D. Sun, Y. Fang, The highly selective oxidation of cyclohexane to cyclohexanone and cyclohexanol over VAlPO4 berlinite by oxygen under atmospheric pressure. Chem. Cent. J. 12(1), 1–9 (2018)10.1186/s13065-018-0405-6 ↗
4. F. Steyer, K. Sundmacher, Cyclohexanol production via esterification of cyclohexene with formic acid and subsequent hydration of the EsterReaction kinetics. Ind. Eng. Chem. Res. 46(4), 1099–1104 (2007)10.1021/ie060781y ↗
5. F. Steyer, H. Freund, K. Sundmacher, A novel reactive distillation process for the indirect hydration of cyclohexene to cyclohexanol using a reactive entrainer. Ind. Eng. Chem. Res. 47(23), 9581–9587 (2008)10.1021/ie800303k ↗
6. B. Wang et al., Sulfamic acid as a green, efficient, recyclable and reusable catalyst for direct addition of aliphatic acid with cyclic olefins. Catal. Lett. 96(1), 71–74 (2004)10.1023/B:CATL.0000029532.80684.6c ↗
7. Y. Leng et al., Sulfonated organic heteropolyacid salts: Recyclable green solid catalysts for esterifications. J. Mol. Catal. A: Chem. 313(1–2), 1–6 (2009)10.1016/j.molcata.2009.08.011 ↗
8. X. Hu et al., Mild acid functionalization of metal-organic framework and its catalytic effect on esterification of acetic acid with n-butanol. Mol. Catal. 482, 110635 (2020)10.1016/j.mcat.2019.110635 ↗
9. M. Ding et al., Carbon capture and conversion using metal–organic frameworks and MOF-based materials. Chem. Soc. Rev. 48(10), 2783–2828 (2019)10.1039/C8CS00829A ↗
10. Q. Wang, D. Astruc, State of the art and prospects in metal-organic framework (MOF)-based and MOF-derived nanocatalysis. Chem. Rev. 120(2), 1438–1511 (2020)10.1021/acs.chemrev.9b00223 ↗
11. Z. Gu, G. Wang, X. Yan, MOF-5 metal−organic framework as sorbent for in-field sampling and preconcentration in combination with thermal desorption GC/MS for determination of atmospheric formaldehyde. Anal. Chem. 82(4), 1365–1370 (2010)10.1021/ac902450f ↗
12. S.S. Nadar et al., Polysaccharide based metal organic frameworks (polysaccharide–MOF): a review. Coord. Chem. Rev. 396, 1–21 (2019)10.1016/j.ccr.2019.05.011 ↗
13. S.S. Nadar, V.K. Rathod, One pot synthesis of α-amylase metal organic framework (MOF)-sponge via dip-coating technique. Int. J. Biol. Macromol. 138, 1035–1043 (2019)10.1016/j.ijbiomac.2019.07.099 ↗
14. B. Li et al., Metal-organic framework based upon the synergy of a Brønsted acid framework and Lewis acid Centers as a highly efficient heterogeneous catalyst for fixed-bed reactions. J. Am. Chem. Soc. 137(12), 4243–4248 (2015)10.1021/jacs.5b01352 ↗
15. Z. Hasan, J.W. Jun, S.H. Jhung, Sulfonic acid-functionalized MIL-101(Cr): An efficient catalyst for esterification of oleic acid and vapor-phase dehydration of butanol. Chem. Eng. J. 278, 265–271 (2015)10.1016/j.cej.2014.09.025 ↗
16. O.V. Gutov et al., Metal-organic framework (MOF) defects under control: insights into the missing linker sites and their implication in the reactivity of zirconium-based frameworks. Inorg. Chem. 54(17), 8396–8400 (2015)10.1021/acs.inorgchem.5b01053 ↗
17. M. Kandiah et al., Synthesis and stability of tagged UiO-66 Zr-MOFs. Chem. Mater. 22(24), 6632–6640 (2010)10.1021/cm102601v ↗
18. H. Jiang et al., Acid regulation of defective sulfonic-acid-functionalized UiO-66 in the esterification of cyclohexene with formic acid. Catal. Lett. (2022). https://doi.org/10.1007/s10562-022-04028-w10.1007/s10562-022-04028-w ↗
19. F.G. Cirujano, A. Corma, F.X. Llabrés I Xamena, Conversion of levulinic acid into chemicals: synthesis of biomass derived levulinate esters over Zr-containing MOFs. Chem. Eng. Sci. 124, 52–60 (2015)10.1016/j.ces.2014.09.047 ↗
20. L. Valenzano et al., Disclosing the complex structure of UiO-66 metal organic framework: a synergic combination of experiment and theory. Chem. Mater. 23(7), 1700–1718 (2011)10.1021/cm1022882 ↗
21. W. Pratanpornlerd, S. Bureekaew, Zr-based metal-organic framework with dual Brønsted acid-base functions. IOP Conf. Ser. Mater. Sci. Eng. 383(1), 12011 (2018)10.1088/1757-899X/383/1/012011 ↗
22. F.M. Lin et al., Ligand-based solid solution approach to stabilisation of sulphonic acid groups in porous coordination polymer Zr6O4(OH)4(BDC)6 (UiO-66). Dalton Trans. 41(45), 13791–13794 (2012)10.1039/c2dt31195j ↗
23. M.J. Cliffe et al., Correlated defect nanoregions in a metal–organic framework. Nat. Commun. 5(1), 1–8 (2014)10.1038/ncomms5176 ↗
24. J.M. Taylor et al., Defect control to enhance proton conductivity in a metal-organic framework. Chem. Mater. 27(7), 2286–2289 (2015)10.1021/acs.chemmater.5b00665 ↗
25. J.M. Taylor et al., The role of a three dimensionally ordered defect sublattice on the acidity of a sulfonated metal-organic framework. J. Am. Chem. Soc. 137(35), 11498–11506 (2015)10.1021/jacs.5b07267 ↗
26. H. Molavi et al., Evaluation of UiO-66 metal organic framework as an effective sorbent for Curcumin’s overdose. Appl. Organomet. Chem. 32(4), e4221 (2018)10.1002/aoc.4221 ↗
27. O.I. Lebedev et al., First direct imaging of giant pores of the metal−organic framework MIL-101. Chem. Mater. 17(26), 6525–6527 (2005)10.1021/cm051870o ↗
28. L. Qiu et al., Hierarchically micro- and mesoporous metal-organic frameworks with tunable porosity. Angew. Chem. Int. Ed. 47(49), 9487–9491 (2008)10.1002/anie.200803640 ↗