Journal of Materials Science

, Volume 54, Issue 13, pp 9466–9477 | Cite as

Mesoporous amorphous TiO2 shell-coated ZIF-8 as an efficient and recyclable catalyst for transesterification to synthesize diphenyl carbonate

  • Bingying Jia
  • Ping Cao
  • Hua Zhang
  • Gongying WangEmail author
Chemical routes to materials


The catalysts containing tetra-coordinated titanium have been widely used for transesterification. The key issue in the design of these catalysts is the stability of tetra-coordinated titanium. In this study, mesoporous amorphous titanium oxides coated on a zeolitic imidazolate framework (ZIF-8) were developed by using a hexadecylamine (HDA) surfactant as a structure-directing agent. The mesopores surface areas of the amorphous TiO2 shell could be simply controlled by changing the dosage of HDA in the synthetic process. The novel, efficient and recyclable heterogeneous catalyst was introduced to the synthesis of diphenyl carbonate from dimethyl carbonate and phenyl acetate for the first time. The catalyst structure was characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, nitrogen adsorption–desorption, Fourier transform infrared spectroscopy and thermogravimetric analysis. The effects of the molar ratio of Ti to Zn, HDA amount, catalyst amount, reaction time and reusability on the yield of the transesterification products were also determined. The results showed that the mesopores of TiO2 shell facilitated reactants and productions diffusion to increase the conversion of phenyl acetate and yield of diphenyl carbonate. Moreover, the coordination between titanium and ZIF-8 also endowed the catalysts with reasonable reusability.



We gratefully acknowledge financial support from the Department of Science and Technology of Sichuan Province (No. 2018CC0139).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflicts of interest.

Supplementary material

10853_2019_3595_MOESM1_ESM.docx (966 kb)
Supplementary material 1 (DOCX 965 kb)


  1. 1.
    Yuan X, Zhang M, Chen X, An N, Liu G, Liu Y, Zhang W, Yan W et al (2012) Transesterification of dimethyl oxalate with phenol over nitrogen-doped nanoporous carbon materials. Appl Catal A Gen 439–440:149–155CrossRefGoogle Scholar
  2. 2.
    Chen T, Han H, Yao J, Wang G (2007) The transesterification of dimethyl carbonate and phenol catalyzed by 12-molybdophosphoric salts. Catal Commun 8:1361–1365CrossRefGoogle Scholar
  3. 3.
    Zhou W, Zhao X, Wang Y, Zhang J (2004) Synthesis of diphenyl carbonate by transesterification over lead and zinc double oxide catalyst. Appl Catal A Gen 260:19–24CrossRefGoogle Scholar
  4. 4.
    Zhang L, He Y, Yang X, Yuan H, Du Z, Wu Y (2015) Oxidative carbonylation of phenol to diphenyl carbonate by Pd/Mo–MnFe2O4 magnetic catalyst. Chem Eng J 278:129–133CrossRefGoogle Scholar
  5. 5.
    Yang X, Hu Y, Bai H, Feng M, Yan Z, Cao S, Yang B (2018) Tuning of oxygen species and active Pd2+ species of supported catalysts via morphology and Mn doping in oxidative carbonylation of phenol. Molecular Catalysis 457:1–7CrossRefGoogle Scholar
  6. 6.
    Cao P, Yang X, Tang C, Yang J, Yao J, Wang Y, Wang G (2009) Molybdenum trioxide catalyst for transesterification of dimethyl carbonate and phenyl acetate to diphenyl carbonate. Chin J Catal 30:853–855CrossRefGoogle Scholar
  7. 7.
    Gao Y, Li Z, Su K, Cheng B (2016) Excellent performance of TiO2(B) nanotubes in selective transesterification of DMC with phenol derivatives. Chem Eng J 301:12–18CrossRefGoogle Scholar
  8. 8.
    Krishna MD, Ziyauddin SQ, Kishor PD, Bhalchandra MB (2010) Transesterification of dimethyl carbonate with phenol using Brønsted and Lewis acidic ionic liquids. Catal Commun 12:207–211CrossRefGoogle Scholar
  9. 9.
    Gabriel CZ, José AVC, César RM, Gianni AP, Juan GSH, Jesus RAA (2017) Comparison of intensified reactive distillation configurations for the synthesis of diphenyl carbonate. Energy 135:637–649CrossRefGoogle Scholar
  10. 10.
    Kim YT, Park ET (2009) Transesterification between dimethyl carbonate and phenol in the presence of (NH4)8Mo10O34 as a catalyst precursor. Appl Catal A Gen 361:26–31CrossRefGoogle Scholar
  11. 11.
    Yang H, Xiao Z, Qu Y, Chen T, Chen Y, Wang G (2018) The role of RGO in TiO2–RGO composites for the transesterification of dimethyl carbonate with phenol to diphenyl carbonate. Res Chem Intermed 44:799–812CrossRefGoogle Scholar
  12. 12.
    Tang R, Chen T, Chen Y, Zhang Y, Wang G (2014) Core-shell TiO2@SiO2 catalyst for transesterification of dimethyl carbonate and phenol to diphenyl carbonate. Chin J Catal 35:457–461CrossRefGoogle Scholar
  13. 13.
    Qu Y, Yang H, Wang S, Chen T, Wang G (2017) High selectivity to diphenyl carbonate synthesized via transesterification between dimethyl carbonate and phenol with C60-doped TiO2. Chem Res Chin Univ 33:804–810CrossRefGoogle Scholar
  14. 14.
    Shaikh AG, Sivaram S (1992) Dialkyl and diaryl carbonates by carbonate interchange reaction with dimethyl carbonate. Ind Eng Chem Res 31:1167–1170CrossRefGoogle Scholar
  15. 15.
    Niu H, Yao J, Wang G (2007) Transesterification of dimethyl carbonate and phenol to diphenyl carbonate catalyzed by titanocene complexes. Catal Commun 8:355–358CrossRefGoogle Scholar
  16. 16.
    Zhou X, Ge X, Tang R, Chen T, Wang G (2014) Preparation and catalytic property of modified multi-walled carbon nanotube-supported TiO2 for the transesterification of dimethyl carbonate with phenol. Chin J Catal 35:481–489CrossRefGoogle Scholar
  17. 17.
    Bian L, Zhang GL (2011) Catalytic performances of silicon dioxide supported titania as catalyst in transesterification between diethyl oxalate and phenol. Adv Mater Res 396–398:724–729CrossRefGoogle Scholar
  18. 18.
    Han H, Chen T, Yao J, Wang G (2006) A heterogeneous catalyst for the transesterification of dimethyl carbonate and phenol to form diphenyl carbonate. Chin J Catal 27:7–8CrossRefGoogle Scholar
  19. 19.
    Chen SY, Mochizuki T, Abe Y, Toba M, Yoshimura Y (2014) Ti-incorporated SBA-15 mesoporous silica as an efficient and robust Lewis solid acid catalyst for the production of high-quality biodiesel fuels. Appl Catal B Environ 148–149:344–356CrossRefGoogle Scholar
  20. 20.
    Wang S, Shi Y, Ma X (2012) Microwave synthesis, characterization and transesterification activities of Ti-MCM-41. Microporous Mesoporous Mater 156:22–28CrossRefGoogle Scholar
  21. 21.
    Sharma RV, Baroi C, Dalai AK (2014) Production of biodiesel from unrefined canola oil using mesoporous sulfated Ti-SBA-15 catalyst. Catal Today 237:3–12CrossRefGoogle Scholar
  22. 22.
    Kim TW, Kim MJ, Kleitz F, Nair MM, Nicolas RG, Jeong KE, Chae HJ, Kim CU et al (2012) Tailor-made mesoporous Ti-SBA-15 catalysts for oxidative desulfurization of refractory aromatic sulfur compounds in transport fuel. ChemCatChem 4:687–697CrossRefGoogle Scholar
  23. 23.
    Parmila D, Umashankar D, Dalai AK (2018) Production of glycerol carbonate using a novel Ti-SBA-15 catalyst. Chem Eng J 346:477–488CrossRefGoogle Scholar
  24. 24.
    Léon CIS, Song D, Su F, An S, Liu H, Gao J, Guo Y, Leng J (2015) Propylsulfonic acid and methyl bifunctionalized TiSBA-15 silica as an efficient heterogeneous acid catalyst for esterification and transesterification. Microporous Mesoporous Mater 204:218–225CrossRefGoogle Scholar
  25. 25.
    Park KS, Zheng N, Adrien PC (2006) Exceptional chemical and thermal stability of zeolitic imidazolate frameworks. PNAS 103:10186–10191CrossRefGoogle Scholar
  26. 26.
    Huang XC, Lin YY, Zhang JP, Chen XM (2006) Ligand-directed strategy for zeolite-type metal-organic frameworks: zinc(II) imidazolates with unusual zeolitic topologies. Angew Chem Int Ed 45:1557–1559CrossRefGoogle Scholar
  27. 27.
    Chizallet C, Bats N (2009) External surface of zeolite imidazolate frameworks viewed ab initio: multifunctionality at the organic-inorganic interface. J Phys Chem Lett 1:349–353CrossRefGoogle Scholar
  28. 28.
    Zhou X, Zhang HP, Wang GY, Yao ZG, Tang YR, Zheng SS (2013) Zeolitic imidazolate framework as efficient heterogeneous catalyst for the synthesis of ethyl methyl carbonate. J Mol Catal A: Chem 366:43–47CrossRefGoogle Scholar
  29. 29.
    Yang L, Yu L, Sun M, Gao C (2014) Zeolitic imidazole framework-67 as an efficient heterogeneous catalyst for the synthesis of ethyl methyl carbonate. Catal Commun 54:86–90CrossRefGoogle Scholar
  30. 30.
    Zeng X, Huang L, Wang C, Wang J, Li J, Luo X (2016) Sonocrystallization of ZIF-8 on electrostatic spinning TiO2 nanofibers surface with enhanced photocatalysis property through synergistic effect. ACS Appl Mater Interfaces 8:20274–20282CrossRefGoogle Scholar
  31. 31.
    Xu X, Li Y, Gong Y, Li H, Wang Y (2012) Synthesis of palladium nanoparticles supported on mesoporous N-doped carbon and their catalytic ability for biofuel upgrade. J Am Chem Soc 134:16987–16990CrossRefGoogle Scholar
  32. 32.
    Cravillon J, Münzer S, Lohmeier SJ, Feldhoff A, Huber K, Wiebcke M (2009) Rapid room-temperature synthesis and characterization of nanocrystals of a prototypical zeolitic imidazolate framework. Chem Mater 21:1410–1412CrossRefGoogle Scholar
  33. 33.
    Guan BY, Yu L, Li J, Lou XW (2016) A universal cooperative assembly-directed method for coating of mesoporous TiO2 nanoshells with enhanced lithium storage properties. Sci Adv 2:1–8Google Scholar
  34. 34.
    Chen D, Cao L, Huang F, Imperia P, Cheng YB, Caruso RA (2010) Synthesis of monodisperse mesoporous titania beads with controllable diameter, high surface areas, and variable pore diameters (14–23 nm). J Am Chem Soc 132:4438–4444CrossRefGoogle Scholar
  35. 35.
    Wang Y, Ma C, Sun X, Li H (2003) Synthesis and characterization of mesoporous TiO2 with wormhole-like framework structure. Appl Catal A Gen 246:161–170CrossRefGoogle Scholar
  36. 36.
    Guan B, Wang T, Zeng S, Wang X, An D, Wang D, Cao Y, Ma D et al (2014) A versatile cooperative template-directed coating method to synthesize hollow and yolk-shell mesoporous zirconium titanium oxide nanospheres as catalytic reactors. Nano Res 7:246–262CrossRefGoogle Scholar
  37. 37.
    Liu P, Liu S, Bian SW (2017) Core–shell-structured Fe3O4/Pd@ZIF-8 catalyst with magnetic recyclability and size selectivity for the hydrogenation of alkenes. J Mater Sci 52:12121–12130. CrossRefGoogle Scholar
  38. 38.
    Zhang R, Elzatahry AA, Al-Deyab SS, Zhao D (2012) Mesoporous titania: from synthesis to application. Nano Today 7:344–366CrossRefGoogle Scholar
  39. 39.
    Antonelli DM, Ying JY (1995) Synthesis of hexagonally packed mesoporous TiO2 by a modified sol–gel method. Angew Chem Int Ed 34:2014–2018CrossRefGoogle Scholar
  40. 40.
    Song H, You JA, Li B, Chen C, Huang J, Zhang J (2017) Synthesis, characterization and adsorptive denitrogenation performance of bimodal mesoporous Ti-HMS/KIL-2 composite: a comparative study on synthetic methodology. Chem Eng J 327:406–417CrossRefGoogle Scholar
  41. 41.
    Yang J, Zhang F, Lu H et al (2015) Hollow Zn/Co ZIF particles derived from core-shell ZIF-67@ZIF-8 as selective catalyst for the semi-hydrogenation of acetylene. Angew Chem Int Ed 54:10889–10893CrossRefGoogle Scholar
  42. 42.
    Liu X, Zou F, Liu K et al (2017) A binary metal organic framework derived hierarchical hollow Ni3S2/Co9S8/N-doped carboncomposite with superior sodium storage performance. J Mater Chem A 5:11781–11787CrossRefGoogle Scholar
  43. 43.
    Poungsombate A, Imyen T, Dittanet P, Embley B, Kongkachuichay P (2017) Direct synthesis of dimethyl carbonate from CO2 and methanol by supported bimetallic Cu–Ni/ZIF-8 MOF catalysts. J Taiwan Inst Chem Eng 80:16–24CrossRefGoogle Scholar
  44. 44.
    Mukhopadhyay S, Debgupta J, Singh C, Kar A, Das SK (2018) A keggin polyoxometalate shows water oxidation activity at neutral pH: POM@ZIF-8, an efficient and robust electrocatalyst. Angew Chem Int Ed 57:1918–1923CrossRefGoogle Scholar
  45. 45.
    Mandana S, Fazaeli R, Aliyan H (2016) Nanostructured sodium-zeolite imidazolate framework (ZIF-8) doped with potassium by sol–gel processing for biodiesel production from soybean oil. J Sol–Gel Sci Technol 77:404–415CrossRefGoogle Scholar
  46. 46.
    Chizallet C, Lazare S, Bazer-Bachi D, Bonnier F, Lecocq V, Soyer E, Quoineaud AA, Bats N (2010) Catalysis of transesterification by a nonfunctionalized metal–organic framework: acido-basicity at the external surface of ZIF-8 probed by FTIR and ab initio calculations. J Am Chem Soc 132:12365–12377CrossRefGoogle Scholar
  47. 47.
    Qu Y, Wang S, Chen T, Wang G (2017) Zn-promoted synthesis of diphenyl carbonate via transesterification over Ti–Zn double oxide catalyst. Res Chem Intermed 43:2725–2735CrossRefGoogle Scholar
  48. 48.
    Şahin F, Topuz B, Kalıpçılar H (2018) Synthesis of ZIF-7, ZIF-8, ZIF-67 and ZIF-L from recycled mother liquors. Microporous Mesoporous Mater 261:259–267CrossRefGoogle Scholar
  49. 49.
    Wang S, Tang R, Zhang Y, Chen T, Wang G (2015) 12-Molybdophosphoric acid supported on titania: a highly active and selective heterogeneous catalyst for the transesterification of dimethyl carbonate and phenol. Chem Eng Sci 138:93–98CrossRefGoogle Scholar

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Authors and Affiliations

  1. 1.Chengdu Institute of Organic ChemistryChinese Academy of SciencesChengduChina
  2. 2.National Engineering Laboratory for VOCs Pollution Control Material and TechnologyUniversity of Chinese Academy of SciencesBeijingChina
  3. 3.School of Chemical EngineeringChongqing University of TechnologyChongqingChina

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