- Research Article
- Open Access
Synthesis and characterization of TiO2-V2O5-MCM-41 for catalyzing transesterification of dimethyl carbonate with phenol
© The Author(s) 2018
- Received: 13 January 2018
- Accepted: 9 October 2018
- Published: 20 October 2018
A series of TiO2-V2O5-MCM-41 molecular sieve catalysts were prepared by the impregnation method. The prepared catalysts were characterized by different techniques including X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and N2 adsorption–desorption. These catalysts were applied in the catalytic synthesis of diphenyl carbonate (DPC) by the transesterification of dimethyl carbonate (DMC) with phenol. The synthesis results indicated that the catalysts possessed the high specific surface area and large pore volume and included titanium with four ligands. Due to the vanadium introduction into Ti-MCM-41, the catalytic activity was promoted, by-products were reduced, and the catalytic activity and stability of the catalyst were significantly improved. With 10%V-20%Ti-MCM-41 catalyst, the optimal synthesis results including the conversion rate of DMC of 33.88%, the selectivity of DPC of 35.84%, and the yield of DPC of 12.14% were obtained.
- Diphenyl carbonate
- Dimethyl carbonate
Diphenyl carbonate (DPC) is a green engineering thermoplastic intermediate widely used in the formation of various organic and polymeric materials, particularly in the synthesis of polycarbonate by the melt transesterification process . The synthesis processes of DPC include the phosgene processes, carbonyl-action of phenol and CO2, and oxidative carbonylation of phenol and transesterification [2–4].
Recently, the heterogeneous catalytic has become a hot topic for the transesterification of DMC and phenol. The reported heterogeneous catalysts include single or composite oxides , zeolites , hydrotalcite-like compounds , and heteropoly compounds . Tong et al. found that V2O5 had the excellent activity for the transesterification of DMC with phenol . Other groups presented that Pb3O4/ZnO, PbO/MgO, and V2O5 as catalysts contributed to the synthesis of DPC . Tang and coworkers proposed that TiO2@SiO2 possessed the favorable catalytic performance . Zhang and coworkers reported that MoO3/SiO2 showed a high activity for both transesterification and disproportionation . In 1992, the Mobil Company in the United States of America invented M41S series of mesoporous molecular sieves which showed the attractive prospect for the shape-selective catalytic oxidation of organic macromolecular materials . Li reported that MoO3/SiMCM-41 shows prominent activity for transesterification .
In this study, a series of TiO2-V2O5-MCM-41 was designed and prepared. All the compositions were characterized by X-ray powder diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and N2 adsorption–desorption. We further explored the catalytic performance of the transesterification reaction of DMC and phenol and verified that TiO2-V2O5-MCM-41 was an efficient catalyst for the transesterification of DMC with phenol.
Tetraethyl orthosilicate (TEOS), cetyl trimethyl ammonium bromide (CTAB), ammonium metavanadate, tetrabutyl titanate, ethanol, ammonia water, phenol, and dimethyl carbonate were of analytical grades and directly used.
Preparation of catalysts
Preparation of Si-MCM-41
The MCM-41 was synthesized based on the previous method . Firstly, 2.0 g CTAB was dissolved in 65.0 g deionized water at a constant temperature of 40 °C. After stirring the mixture for half an hour, 20.0 g ammonia water was added into the solution, followed by 30-min stirring. Then, 8.5 g TEOS was dropped slowly into the mixture for 2-h stirring. After the reaction, the resulting product was aged at ambient temperature for 24 h and then crystallized at 110 °C for 24 h in the reaction kettle. The product was filtered, washed with deionized water, air-dried, and calcined in air at 300 °C for 2.5 h and 650 °C for 3.5 h. Finally, the white powder product was obtained and named Si-MCM-41.
Preparation of Ti-MCM-41
The tetrabutyl titanate was dissolved in the ethanol as the precursor of Ti. The mixture was stirred for 15–20 min. Then the MCM-41 was added into the solution. The MCM-41 was fully impregnated. Then the mixture was air-dried and calcined in air at 120 °C for 4 h and 550 °C for 5 h. Thus, the white powder product of mesoporous silica material was obtained and named Ti-MCM-41. The samples with different titanium loadings were obtained by changing the mole percentages of tetrabutyl titanate and MCM-41.
Preparation of Ti-V-MCM-41
A certain amount of ammonium metavanadate was firstly dissolved in dilute ammonia water. Then the Ti-MCM-41 was added into the solution and fully impregnated. Water and ammonia were evaporated. The obtained mixture was vacuum-desiccated at 100 °C for 3 h, and then calcined in air at 500 °C for 3 h. The samples with different vanadium contents were obtained by changing the mole percentages of ammonium metavanadate, tetrabutyl titanate, and MCM-41.
X-ray diffraction (XRD) patterns of the samples were obtained by using a Rigaku D/max-2500 X-ray diffractometer under Cu-Kα radiation at 40 kV and 100 mA. The diffraction data were collected every 0.02° at a scan speed of 1°(2θ)/min from 1° to 10° and 10° to 60°, respectively.
N2 adsorption–desorption isotherms were recorded at 77 K on a Micromeritics ASAP 2020. The samples were dried at 200 °C for 8 h before the measurement. BET surface areas were calculated from the linear part of the BET plot. The pores size distribution is calculated from desorption branche of the nitrogen adsorption.
Fourier-transform infrared spectroscopy (FT-IR) analysis were performed on a VERTEX 70 infrared spectrometer with KBr pellets in the infrared region of 4000 ~ 500 cm−l.
X-ray photoelectron spectroscopy (XPS) was measured on a VG ESCALAB5 multi-function electronic energy spectrometer with Al-Kα ray under CAE mode. The spectrometer was operated with a tube voltage of 9 kV and a tube current of 18.5 mA.
Transmission electron microscopy (TEM) experiments were conducted on a JEM-3010.
The transesterification of DMC with phenol was conducted in a 100-mL three-neck round-bottomed flask under nitrogen atmosphere. In a typical experiment, a certain amount of phenol and catalyst were added into the flask under the stirring conditions at slowly increasing temperature. When the temperature reached 180 °C, DMC was introduced dropwise. The reaction temperature was maintained at 180 °C and the reaction mixture was treated under the refluxing condition at 180 °C. In the transesterification reaction, a distillate of DMC and methanol was collected slowly in a receiver flask attached to the liquid dividing head for analysis. After the reaction, the mixture was cooled to ambient temperature. The catalyst was regained by filtration and the filtrate was analyzed by gas chromatography.
The azeotrope of DMC and methanol and the reaction system were analyzed by gas chromatography equipped with a capillary column (30 m) and a flame ionization detector (FID). The identification analysis of the reaction system was conducted on a 6890/5973 GC–Mass spectrometer.
The strong and broad peak at 2θ = 23° is observed in Fig. 2. The XRD pattern of Ti-MCM-41 is similar to that of MCM-41, indicating that the ordered hexagonal porous framework is retained after grafting titanium atom onto MCM-41. The slight changes of absorption peak intensity and peak position indicate that the metallic elements have entered into the framework of zeolite and changed the long-range order of silicon molecular sieve. In the XRD patterns of Ti-MCM-41, the characteristic peaks slightly decrease after loading titanium atom onto MCM-41. In contrast to Fig. 2, the spectra is not obviously changed even when the initial titanium loading increases up to 40 wt% in the synthesis solution, indicating that the titanium has been evenly dispersed into the catalyst.
Pore structure and specific surface area
Pore structure analysis of samples
Pore volume (cm3/g)
BJH pore size (nm)
X-ray photoelectron spectroscopy analysis
The evaluation experiment of the catalyst was carried out in a reactive distillation unit. Reaction conditions were set as follows: phenol (30.0 g); DMC (30.0 g), catalyst (0.5 g), reaction temperature (180 °C), and reaction time (8 h). The conversion rate of raw materials is low in the blank experiment, whereas the conversion and selectivity are improved obviously after adding the catalysts.
In summary, a series of Ti-V-MCM-41 catalysts were prepared by grafting titanium and vanadium atoms on the surface of MCM-41. Ti-V-MCM-41 catalyst showed the excellent catalytic activity and selectivity for the transesterification reaction between phenol and DMC. Among the obtained catalysts, an appropriate amount of Ti (20%) and V (10%) supported on MCM-41 gave the best results to produce MPC and DPC in the yields of 21.74% and 12.14%. The mesoporous structure of MCM-41 molecular sieve was maintained in all samples and promoted the reaction selectivity. The different measurements indicated that the metallic elements (Ti) entered the framework of zeolite and formed Si–O–Ti bond. The titanium of catalyst still existed in the form of Ti(IV) species until Ti loading reached 20%. After the vanadium was introduced into Ti-MCM-41, it promoted the catalytic activity, reduced the by-products, and significantly improved the catalytic activity and stability of the catalysts. The vanadium pentoxide in the catalyst played a catalytic or coordinating role. In a word, the 10%V-20%Ti-MCM-41 catalyst is a promising catalyst for the transesterification of DMC and phenol.
Jinfeng Zhang conceived and designed the study. Jinfeng Zhang, YG and HS performed the experiments. Jinfeng Zhang wrote the paper. Jiyao Zhang and Jianshe Zhao reviewed and edited the manuscript. All authors read and approved the final manuscript.
All authors declare that they have no competing interests.
This study was funded by National Natural Science Foundation of China (Grant Nos. 21371143; 21671157).
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Open AccessThis article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The Creative Commons Public Domain Dedication waiver (http://creativecommons.org/publicdomain/zero/1.0/) applies to the data made available in this article, unless otherwise stated.
- Fukuoka S, Kawamura M, Komiya K et al (2003) A novel non-phosgene polycarbonate production process using by-product CO2 as starting material. J Green Chem 5(5):497–507View ArticleGoogle Scholar
- Kim WB, Joshi UA, Lee JS (2004) Making polycarbonates without employing phosgene: an overview on catalytic chemistry of intermediate and precursor syntheses for polycarbonate. J Ind Eng Chem Res 43(9):1897–1914View ArticleGoogle Scholar
- Li Z, Qin Z, Zhu H et al (2006) Synthesis of diphenyl carbonate from CO2, phenoxide, and CCl4 with ZnCl2 as catalyst. J Chem Lett 35(7):784–785View ArticleGoogle Scholar
- Kim WB, Park ED, Lee JS (2003) Effects of inorganic cocatalysts and initial states of Pd on the oxidative carbonylation of phenols over heterogeneous Pd/C. J Appl Catal A General 242(2):335–345View ArticleGoogle Scholar
- Kim YT, Park ED (2009) Deactivation phenomena of MoO3/SiO2 and TiO2/SiO2 during transesterification between dimethyl carbonate and phenol. J Appl Catal A General 356(2):211–215View ArticleGoogle Scholar
- Shuwen LUO, Tong C, Dongshen T et al (2007) Synthesis of diphenyl carbonate via transesterification catalyzed by HMS mesoporous molecular sieves containing heteroelements. J Chin J Catal 28(11):937–939View ArticleGoogle Scholar
- Fuming M, Zhi P, Guangxing L (2004) The transesterification of dimethyl carbonate with phenol over Mg-Al-hydrotalcite catalyst. J Org Process Res Dev 8:372–375View ArticleGoogle Scholar
- Chen T, Han H, Yao J et al (2007) The transesterification of dimethyl carbonate and phenol catalyzed by 12-molybdophosphoric salts. J Catal Commun 8(9):1361–1365View ArticleGoogle Scholar
- Tong DS, Yao J, Wang Y et al (2007) Transesterification of dimethyl carbonate with phenol to diphenyl carbonate over V2O5 catalyst. J J Mol Catal A Chem 268(1):120–126View ArticleGoogle Scholar
- Wang S, Bai R, Mei F et al (2009) Pyroaurite as an active, reusable and environmentally benign catalyst in synthesis of diphenyl carbonate by transesterification. J Catal Commun 11(3):202–205View ArticleGoogle Scholar
- Tang R, Chen T, Chen Y et al (2014) Core-shell TiO2@SiO2 catalyst for transesterification of dimethyl carbonate and phenol to diphenyl carbonate. J Chin J Catal 35(4):457–461View ArticleGoogle Scholar
- Wang S, Zhang Y, Chen T et al (2015) Preparation and catalytic property of MoO3/SiO2 for disproportionation of methyl phenyl carbonate to diphenyl carbonate. J J Mol Catal A Chem 398:248–254View ArticleGoogle Scholar
- Arends I, Sheldon RA (2001) Activities and stabilities of heterogeneous catalysts in selective liquid phase oxidations: recent developments. J Appl Catal A General 212(1):175–187View ArticleGoogle Scholar
- Li Z, Cheng B, Su K et al (2008) The synthesis of diphenyl carbonate from dimethyl carbonate and phenol over mesoporous MoO3/SiMCM-41. J J Mol Catal A Chem 289(1):100–105View ArticleGoogle Scholar
- Beck JS, Vartuli JC, Roth WJ et al (1992) A new family of mesoporous molecular sieves prepared with liquid crystal templates. J J Am Chem Soc 114(27):10834–10843View ArticleGoogle Scholar
- Wang S, Ma X et al (2004) Characterization and catalytic activity of TiO2/SiO2 for transesterification of dimethyl oxalate with phenol. J Mol Catal A Chem 214:273–279View ArticleGoogle Scholar
- Tong DS, Yao J et al (2007) Transesterification of dimethyl carbonate with phenol to diphenyl carbonate over V2O5 catalyst. J Mol Catal A Chem 268:120–126View ArticleGoogle Scholar