RSC Advances View Article Online PAPER View Journal | View Issue Highly effective transformation of methyl phenyl carbonate to diphenyl carbonate with recyclable Pb Cite this: RSC Adv.,2019,9,20415 nanocatalyst† Songlin Wang,ab Hongying Niu,a Jianji Wang,b Tong Chen, *c Gongying Wangc and Jiamin Zhanga Diphenyl carbonate (DPC) is a type of versatile industrial chemical, and the disproportionation of methyl phenyl carbonate (MPC) is a key step to produce DPC. However, the design and formulation of a catalyst for the efficient synthesis of DPC is a major challenge due to its small equilibrium constant. The support material is a critical factor influencing the performance of Pb nanocatalysts. Thus, a series of Pb-based catalysts over MgO, ZrO2, SiO2, TiO2 and Al2O3 were prepared to investigate the effect of the support materials on the physicochemical properties and catalytic performances for the conversion of MPC to effectively synthesize DPC. The catalysts were well characterized by XRD, BET, TEM, XPS, ICP-OES, H2- Creative Commons Attribution 3.0 Unported Licence. TPR, Py-IR and NH3-TPD. The results showed that the nature of the support obviously affected the structural properties and catalytic performances, and Pb was dispersed better on SiO2, TiO2, ZrO2 and MgO than on Al2O3, and showed stronger metal-support interaction over MgO and ZrO2. The activity results revealed that PbO/MgO and PbO/ZrO2 exhibited higher catalytic activities because they contained higher Pb dispersion and more Lewis acid sites, and the catalytic activities followed the order PbO/MgO > PbO/ZrO2 > PbO/SiO2 > PbO/Al2O3 > PbO/TiO2. On the contrary, PbO/MgO and PbO/ZrO2 Received 24th May 2019 exhibited better reusability due to strong interaction between the highly dispersed Pb and the supports, Accepted 12th June 2019 and the activity decrease in the case of PbO/SiO2, PbO/Al2O3 and PbO/TiO2 mainly resulted from the Pb DOI: 10.1039/c9ra03931g leaching loss. This work would contribute to exploiting novel catalytic materials in a wide range of This article is licensed under a rsc.li/rsc-advances applications for the efficient synthesis of organic carbonates. 6,7 8,9 Open Access Article. Published on 01 July 2019. Downloaded 9/30/2021 6:26:57 AM. 1. Introduction (phosgene method, oxidative carbonylation, trans- esterication,10,11 etc.), the transesterication of phenol and Due to its outstanding electrical, mechanical and heat resis- dimethyl carbonate (DMC) was regarded as a most likely tance properties, polycarbonate (PC), as an important engi- pathway to synthesize DPC without employing phosgene since neering thermoplastic for ubiquitous applications in several the starting materials presented low toxicity and high biode- industries (automobiles, office equipment, medical devices, gradability. This route consisted in two-step reaction where etc.), has attracted considerable interest in the last decades.1,2 methyl phenyl carbonate (MPC) of the intermediate was rst Diphenyl carbonate (DPC), a building block, was oen produced by the transesterication (Scheme 1-(1)), followed by employed for the phosgene-free synthesis of PC by melt trans- the further transesterication reaction of MPC and phenol esterication with bisphenol-A, and was also used for the production of pharmaceuticals, polymer materials, ne chem- icals, etc.3–5 It was, therefore, necessary to develop efficient and environmentally benign synthetic routes to replace the highly toxic synthesis via phosgene. Among the alternative routes aSchool of Chemistry and Chemical Engineering, Henan Institute of Science and Technology, Xinxiang 453003, P. R. China. E-mail: [email protected] bPostdoctoral Programs, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, P. R. China. E-mail: [email protected] cChengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, P. R. China. E-mail: [email protected] † Electronic supplementary information (ESI) available. See DOI: Scheme 1 Transesterification process between DMC and phenol into 10.1039/c9ra03931g DPC. This journal is © The Royal Society of Chemistry 2019 RSC Adv.,2019,9,20415–20423 | 20415 View Article Online RSC Advances Paper (Scheme 1-(2)) or the disproportionation of MPC (Scheme 1-(3)). 2. Experimental section Concerning the second-step reaction the equilibrium constants 2.1 Material preparation K2 and K3 indicated that DPC was mainly produced by the second step disproportionation instead of the further trans- All chemicals adopted in this work were analytical purity, which esterication.12,13 On the contrary, the rst step was rate- were purchased from Sinopharm Chemical Reagent Co., Ltd determining step since K1 was much lower than K3. Hence, and were directly used as received without further purication. considerable studies on the rst step transesterication have Deionized water was used in all experimental synthesis proce- been particularly carried out,14–17 but only few efforts have been dures as needed. 18,19 – made to the second step disproportionation. Indeed, the Pure SiO2 was synthesized by sol gel process. For this disproportionation of MPC is also the key step to produce DPC. preparation, the desired amounts of tetraethyl orthosilicate, Overall, it is very signicant to intensively study on MPC ethanol and distilled water were mixed together at room disproportionation, which is advantageous to improving the temperature. Then the ammonium aqueous solution was added yield of DPC and the conversion of the starting materials in gradually into the above solution under stirring at 50 Cto future industrial applications. generate a transparent gel. The obtained gel was aged at 50 C The disproportionation reaction suffered from the low yield overnight, dried at 110 C for 12 h and subsequently calcinated and selectivity of DPC due to the relatively low equilibrium 550 C for 5 h. constant and reaction rate. Therefore, the development of Pure TiO2 was prepared by hydrolysis process. Brie y, highly active catalysts is crucial in this reaction. Among various a proper amount of tetrabutyl titanate was dissolved in ethanol, homogeneous catalytic systems reported like organo-tin/ and heated up to 50 C under stirring. Then, appropriate titanium catalysts, even though they exhibited outstanding amount of water was slowly added to promote the hydrolysis catalytic activities,19,20 they had received little consideration and was kept for 24 h. Finally, the sediment was ltered, washed because of the separation problems between DPC and the with distilled water, and dried at 110 C for 12 h and calcinated Creative Commons Attribution 3.0 Unported Licence. catalysts. Therefore, heterogeneous catalysis currently attracted at 550 C for 5 h. more attention because these catalysts might be facilely recov- Pure Al2O3 was prepared by a precipitation process. A certain ered from the reaction mixture by simple ltration and could be amount of aluminum nitrate nonahydrate were dissolved in the recycled, making the procedure more feasible. deionized water and heated slowly to 90 C. Aerwards, Recently, we studied the catalytic performances of various ammonia solution with 25% concentration was added into this 21–23 metal oxides including TiO2, MoO3, PbO and so on, and solution under stirring until that the pH of 9–10 was reached. found that PbO was prepared into the supported Pb catalysts or The as-prepared solid sediment was aged for 24 h and then mixed metal oxides signicantly improved the catalytic activity, vacuum ltered off and washed repeatedly. Finally, the obtained life time and stability.24,25 However, the nature and property of samples were dried at 110 C for 12 h and subsequently calci- This article is licensed under a the support is o en found to modify the distribution, loading, nated at 550 C for 5 h. Likewise, pure MgO and ZrO2 were size, shape and electronic state of the active species as well as prepared by using the similar process, respectively. their interactions with support with some special physical– The preparation of supported Pb-based catalysts was carried Open Access Article. Published on 01 July 2019. Downloaded 9/30/2021 6:26:57 AM. ff chemical properties, which is well known to strongly a ect the out by incipient wetness impregnation process. Briey, SiO2, 26–31 catalytic activity and stability. Therefore, the study to TiO2,Al2O3, ZrO2 and MgO supports were homogeneously investigate the structure–function relationship of the supports impregnated by using the aqueous solution of lead nitrate as on Pb-based catalysts for MPC disproportionation is very precursor salt at ambient temperature for 24 h, respectively. worthwhile, which is conducive to screen suitable and prom- Aer impregnation, the samples were dried in air at 110 C for ising supports. 12 h, and nally calcinated at 550 C for 5 h. And the PbO In the present work, we formulate Pb-based catalysts by loading used was 10 wt% for all the catalysts. employing potential metal oxides as support phases and focus on studying the effect of various supports on the physico- 2.2 Material characterization chemical properties of the catalysts and their catalytic perfor- mance to provide the role of support materials for developing The X-ray powder diffraction (XRD) analysis was carried out on efficient catalysis materials for MPC disproportionation to a DX-2700B diffractometer with the Ni-ltered CuKa radiation effectively synthesize DPC. Herein the Pb-based catalysts are (1.5418 A).˚ The X-ray tube was operated at 40 kV and 30 mA, and prepared using wet-impregnation process over PbO loading the powder diffractogram was recorded at 0.02 intervals in the À1 onto SiO2, TiO2,Al2O3, MgO and ZrO2 supports. At the same range of 5–90 with the scanning rate of 1.2 min . time, the catalysts are thoroughly characterized by X-ray The determination of the elemental composition was con- ff di raction (XRD), temperature programmed reduction of H2 ducted by Optima 2000 DV inductively coupled plasma-optical (H2-TPR), transmission electron microscopy (TEM), X-ray emission spectrometer (PerkinElmer Inc., USA).