Mechanistic Study on the Dominant Promotion Effect of Al-/Ti-/Zr-modifications over the VOx/SiO2 UHMWPE Catalysts

Citation: Yu-Long Jin, Lin Liu, Yu-Jie Wang, Zhen Liu, Bo-Ping Liu. Mechanistic Study on the Dominant Promotion Effect of Al-/Ti-/Zr-modifications over the VO_x/SiO₂ UHMWPE Catalysts[J]. Chinese Journal of Polymer Science, 2019, 37(10): 995-1004. doi: 10.1007/s10118-019-2295-z shu

Mechanistic Study on the Dominant Promotion Effect of Al-/Ti-/Zr-modifications over the VO_x/SiO₂ UHMWPE Catalysts

通讯作者: , boping@scau.edu.cn

English

Mechanistic Study on the Dominant Promotion Effect of Al-/Ti-/Zr-modifications over the VO_x/SiO₂ UHMWPE Catalysts

a.
College of Materials and Energy, South China Agricultural University, Guangzhou 510642, China
b.
School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

Corresponding author: Bo-Ping Liu, boping@scau.edu.cn

Received Date: 30 March 2019
Accepted Date: 16 May 2019
Revised Date: 13 May 2019
Available Online: 01 October 2019

Abstract: Recently, we reported the first VO_x/SiO₂ ethylene polymerization catalyst for making Cl-free UHMWPE, and found the dominant promotion effects of Al-/Ti-/Zr-modifications over this catalyst system (Macromol. Chem. Phys. 2017, 218, 1600443). In this work, density functional theory is applied to investigate the underlying mechanism of this remarkable promotion effect of Al-/Ti-/Zr-modifications on a molecular and atomic level. The cluster model with V(III) is found to be the most possible active site due to its lowest overall energy barrier for monomer insertion, though the process of C₂H₄ coordination and the subsequent formation of transition state are most energy favored for V(II) species. By modifying one of or both V―O―Si in the active model with V―O―M (M ＝ Al, Ti, or Zr), the energy barrier for the binding of the upcoming C₂H₄ gets lower (particularly for Al- and Zr-modified catalysts), and the transition state also becomes more stable. Generally, the insertion process of C₂H₄ gets easier after support Al-/Ti-/Zr-modifications. This dominant promotion effect is partially ascribed to the more enriched positive charge distribution on or nearby the V center, and the narrower energy gap between the LUMO of model catalysts and the HOMO of C₂H₄ for these modified catalysts also contributes much. In addition, the decreased steric hindrance around the V center should be taken into account for the modified models as well. Furthermore, the Brønsted acidity of the catalysts is investigated by introducing a pendent hydroxyl group to the model catalysts, which has a close contact with the V center. Similar promotion effect of support modification by Al, Ti, and Zr could still be observed.

Key words:

1. [1]
  Weckhuysen, B. M.; Keller, D. E. Chemistry, spectroscopy and the role of supported vanadium oxides in heterogeneous catalysis. Catal. Today 2003, 78, 25-46. doi: 10.1016/S0920-5861(02)00323-1
2. [2]
  Matta, A.; Zeng, Y.; Taniike, T.; Terano, M. Vanadium-modified bimetallic phillips catalyst with high branching ability for ethylene polymerization. Macromol. Reac. Eng. 2012, 6, 346-350. doi: 10.1002/mren.v6.8
3. [3]
  Zeng, Y.; Matta, A.; Dwivedi, S.; Taniike, T.; Terano, M. Development of a hetero-bimetallic Phillips-type catalyst for ethylene polymerization. Macromol. Reac. Eng. 2013, 7, 668-673. doi: 10.1002/mren.v7.12
4. [4]
  Wang, J.; Cheng, R.; He, X.; Liu, Z.; Zhao, N.; Liu, B. Vanadium modification effects on the (SiO₂/MgO/MgCl₂)·TiClx Ziegler-Natta polyethylene catalyst. Macromol. Reac. Eng. 2016, 10, 246-260. doi: 10.1002/mren.201500056
5. [5]
  Cheng, R.; Xue, X.; Liu, W.; Zhao, N.; He, X.; Liu, Z.; Liu, B. Novel SiO₂‐supported chromium oxide (Cr)/vanadium oxide (V) bimetallic catalysts for production of bimodal polyethylene. Macromol. Reac. Eng. 2015, 9, 462-472. doi: 10.1002/mren.v9.5
6. [6]
  Zhao, N.; Cheng, R.; He, X.; Liu, Z.; Liu, B. A novel SiO₂‐supported Cr―V bimetallic catalyst making polyethylene and ethylene/1-hexene copolymers with bimodal molecular weight distribution. Macromol. Chem. Phys. 2014, 1753-1766.
7. [7]
  Liu, B.; Tian, Z.; Zhao, N.; Liu, Z.; Liu, B. Peculiarities of ethylene polymerization kinetics with an imido-vanadium/silyl-chromate bimetallic catalyst: effect of polymerization conditions. Ind. Eng. Chem. Res. 2017, 56, 6164-6175. doi: 10.1021/acs.iecr.7b00883
8. [8]
  Liu, B.; Zhao, N.; Jin, Y.; Cheng, R.; He, X.; Liu, Z.; Liu, B. Effects of alkyl aluminum on SiO₂-supported silyl-chromate(Cr)/imido-vanadium(V) bimetallic catalysts for producing bimodal polyethylene. Macromol. Reac. Eng. 2017, 11, 1700006. doi: 10.1002/mren.v11.5
9. [9]
  Jin, Y.; Zhao, N.; Cheng, R.; He, X.; Liu, Z.; Dong, D.; Bin, Y.; Chen, X.; Li, L.; Liu, B. One pot synthesis of bimodal UHMWPE/HDPE in‐reactor blends with Cr/V bimetallic catalysts. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3404–3412. doi: 10.1002/pola.v55.20
10. [10]
  Jin, Y.; Cheng, R.; He, X.; Liu, Z.; Zhao, N.; Liu, B. The first vanadium-oxide-based UHMWPE catalyst supported on chemically modified silica gel. Macromol. Chem. Phys. 2017, 218, 1600443. doi: 10.1002/macp.v218.7
11. [11]
  McDaniel, M. P. A review of the Phillips supported chromium catalyst and its commercial use for ethylene polymerization. Adv. Catal. 2010, 53, 123-606.
12. [12]
  Gierada, M.; Handzlik, J. Active sites formation and their transformations during ethylene polymerization by the Phillips CrO_x/SiO₂ catalyst. J. Catal. 2017, 352, 314-328. doi: 10.1016/j.jcat.2017.05.025
13. [13]
  Anthony, G.; Alexis, T. B. A theoretical investigation of the selective oxidation of methanol to formaldehyde on isolated vanadate species supported on silica. J. Phys. Chem. C 2008, 112, 13204-13214. doi: 10.1021/jp801339q
14. [14]
  William, C. V.; Anthony, G.; Jennifer, S.; Alexis, T. B. An experimental and theoretical investigation of the structure and reactivity of bilayered VO_x/TiO_x/SiO₂ catalysts for methanol oxidation. J. Catal. 2010, 270, 163-171. doi: 10.1016/j.jcat.2009.12.017
15. [15]
  Cheng, R.; Xu, C.; Liu, Z.; Dong, Q.; He, X.; Fang, Y.; Terano, M.; Hu, Y.; Pullukat, T. J.; Liu, B. High-resolution spectroscopy (XPS, 1H MAS solid-state NMR) and DFT investigations into Ti-modified Phillips CrO_x/SiO₂ catalysts. J. Catal. 2010, 273, 103-115. doi: 10.1016/j.jcat.2010.05.002
16. [16]
  Ma, Y.; Wang, L.; Liu, Z.; Cheng, R.; Zhong, L.; Yang, Y.; He, X.; Fang, Y.; Terano, M.; Liu, B. High-resolution XPS and DFT investigations into Al-modified Phillips CrO_x/SiO₂ catalysts. J. Mol. Catal. A-Chem. 2015, 401, 1-12. doi: 10.1016/j.molcata.2015.01.020
17. [17]
  Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; Li, X.; Caricato, M.; Marenich, A.; Bloino, J.; Janesko, B. G.; Gomperts, R.; Mennucci, B.; Hratchian, H. P.; Ortiz, J. V.; Izmaylov, A. F.; Sonnenberg, J. L.; Williams-Young, D.; Ding, F.; Lipparini, F.; Egidi, F.; Goings, J.; Peng, B.; Petrone, A.; Henderson, T.; Ranasinghe, D.; Zakrzewski, V. G.; Gao, J.; Rega, N.; Zheng, G.; Liang, W.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Throssell, K.; Montgomery, J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Keith, T.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Millam, J. M.; Klene, M.; Adamo, C.; Cammi, R.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Farkas, O.; Foresman, J. B.; Fox, D. J. in Gaussian 09, Revision E.01, Gaussian, Inc., Wallingford, CT, USA. 2016.
18. [18]
  Jeng-Da, C.; Martin, H. G. Long-range corrected hybrid density functionals with damped atom-atom dispersion corrections. Phys. Chem. Chem. Phys. 2008, 10, 6615-6620. doi: 10.1039/b810189b
19. [19]
  Fong, A.; Ye, Y.; Ivry, S. L.; Scott, S. L.; Peters, B. Computational kinetic discrimination of ethylene polymerization mechanisms for the Phillips (Cr/SiO₂) catalyst. ACS Catal. 2015, 5, 9882-9891.
20. [20]
  Weigend, F.; Ahlrichs, R. Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. Phys. Chem. Chem. Phys. 2005, 7, 3297-3305. doi: 10.1039/b508541a
21. [21]
  Gonzalez, C.; Schlegel, H. B. Reaction path following in mass-weighted internal coordinates. J. Phys. Chem. 1990, 94, 5523-5527. doi: 10.1021/j100377a021
22. [22]
  Maeda, S.; Harabuchi, Y.; Ono, Y.; Taketsugu, T.; Morokuma, K. Intrinsic reaction coordinate: Calculation, bifurcation, and automated search. Int. J. Quantum. Chem. 2015, 115, 258-269. doi: 10.1002/qua.24757
23. [23]
  Reed, A. E.; Weinhold, F.; Curtiss, L. A.; Pochatko, D. J. Natural bond orbital analysis of molecular interactions: Theoretical studies of binary complexes of HF, H₂O, NH₃, O₂, F₂, CO, and CO₂ with HF, H₂O, and NH₃. J. Chem. Phys. 1986, 84, 5687-5705. doi: 10.1063/1.449928
24. [24]
  Frank, W. Natural bond orbital analysis: a critical overview of relationships to alternative bonding perspectives. J. Comput. Chem. 2012, 33, 2363-2379. doi: 10.1002/jcc.v33.30
25. [25]
  Tian, L.; Feiwu, C. Multiwfn: a multifunctional wavefunction analyzer. J. Comput. Chem. 2012, 33, 580-592. doi: 10.1002/jcc.v33.5
26. [26]
  Bader, R. F. W.; Carroll, M. T.; Cheeseman, J. R.; Chang, C. Properties of atoms in molecules: atomic volumes. J. Am. Chem. Soc. 1987, 109, 417-423. doi: 10.1021/ja00236a020
27. [27]
  Keller, D. E.; Visser, T.; Soulimani, F.; Koningsberger, D. C.; Weckhuysen, B. M. Hydration effects on the molecular structure of silica-supported vanadium oxide catalysts: A combined IR, Raman, UV-vis and EXAFS study. Vib. Spectrosc. 2007, 43, 140-151. doi: 10.1016/j.vibspec.2006.07.005
28. [28]
  Olthof, B.; Khodakov, A.; Bell, A. T.; Iglesia, E. Effects of support composition and pretreatment conditions on the structure of vanadia dispersed on SiO₂, Al₂O₃, TiO₂, ZrO₂, and HfO₂. J. Phys. Chem. B 2000, 104, 1516-1528. doi: 10.1021/jp9921248
29. [29]
  Tian, H.; Ross, E. I.; Wachs, I. E. Quantitative determination of the speciation of surface vanadium oxides and their catalytic activity. J. Phys. Chem. B 2006, 110, 9593-9600. doi: 10.1021/jp055767y
30. [30]
  Khaliullin, R. Z.; Bell, A. T. A density functional theory study of the oxidation of methanol to formaldehyde over vanadia supported on silica, titania, and zirconia. J. Phys. Chem. B 2002, 106, 7832-7838. doi: 10.1021/jp014695h
31. [31]
  Blasco, T.; Nieto, J. M. L. Oxidative dyhydrogenation of short chain alkanes on supported vanadium oxide catalysts. Appl. Catal. A-Gen. 1997, 157, 117-142. doi: 10.1016/S0926-860X(97)00029-X
32. [32]
  Koten, G. v.; Hagen, H.; Boersma, J. Homogeneous vanadium-based catalysts for the Ziegler-Natta polymerization of α-olefins. Chem. Soc. Rev. 2002, 31, 357-364. doi: 10.1039/B205238E
33. [33]
  Nomura, K.; Zhang, S. Design of vanadium complex catalysts for precise olefin polymerization. Chem. Rev. 2010, 111, 2342-2362.
34. [34]
  Cossee, P. Ziegler-Natta catalysis I. Mechanism of polymerization of α-olefins with Ziegler-Natta catalysts. J. Catal. 1964, 3, 80-88. doi: 10.1016/0021-9517(64)90095-8
35. [35]
  Goldsmith, B. R.; Peters, B.; Johnson, J. K.; Gates, B. C.; Scott, S. L. Beyond ordered materials: Understanding catalytic sites on amorphous solids. ACS Catal. 2017, 7, 7543-7557. doi: 10.1021/acscatal.7b01767
36. [36]
  Lichtenstein, L.; Heyde, M.; Freund, H. J. Atomic arrangement in two-dimensional silica: From crystalline to vitreous structures. J. Phys. Chem. C 2012, 116, 20426-20432. doi: 10.1021/jp3062866
37. [37]
  Büchner, C.; Liu, L.; Stuckenholz, S.; Burson, K. M.; Lichtenstein, L.; Heyde, M.; Gao, H. J.; Freund, H. J. Building block analysis of 2D amorphous networks reveals medium range correlation. J. Non-cryst. Solid. 2016, 435, 40-47. doi: 10.1016/j.jnoncrysol.2015.12.020
38. [38]
  Gao, X.; Bare, S. R.; Weckhuysen, B. M.; Wachs, I. E. In situ spectroscopic investigation of molecular structures of highly dispersed vanadium oxide on silica under various conditions. J. Phys. Chem. B 1998, 102, 10842-10852. doi: 10.1021/jp9826367
39. [39]
  Delley, M. F.; Núñez-Zarur, F.; Conley, M. P.; Comas-Vives, A.; Siddiqi, G.; Norsic, S.; Monteil, V.; Safonova, O. V.; Copéret, C. Proton transfers are key elementary steps in ethylene polymerization on isolated chromium(III) silicates. Proc. Natl. Acad. Sci. U. S. A. 2014, 111, 11624-11629. doi: 10.1073/pnas.1405314111
40. [40]
  Conley, M. P.; Delley, M. F.; Núñez-Zarur, F.; Comas-Vives, A.; Copéret, C. Heterolytic activation of C―H bonds on CrIII-O surface sites is a key step in catalytic polymerization of ethylene and dehydrogenation of propane. Inorg. Chem. 2015, 54, 5065-5078. doi: 10.1021/ic502696n
41. [41]
  Feher, F. J.; Blanski, R. L. Olefin polymerization by vanadium-containing silsesquioxanes: Synthesis of a dialkyl-oxo-vanadium(V) complex that initiates ethylene polymerization. J. Am. Chem. Soc. 1992, 114, 5886-5887. doi: 10.1021/ja00040a076
42. [42]
  Liu, B.; Fang, Y.; Xia, W.; Terano, M. Theoretical investigation of novel silsesquioxane-supported Phillips-type catalyst by density functional theory (DFT) method. Kinet. Catal. 2006, 47, 234-240. doi: 10.1134/S0023158406020121
43. [43]
  Quadrelli, E. A.; Basset, J.-M. On silsesquioxanes’ accuracy as molecular models for silica-grafted complexes in heterogeneous catalysis. Coordin. Chem. Rev. 2010, 254, 707-728. doi: 10.1016/j.ccr.2009.09.031
44. [44]
  Uchino, T.; Tokuda, Y.; Yoko, T. Vibrational dynamics of defect modes in vitreous silica. Phys. Rev. B 1998, 58, 5322-5328.
45. [45]
  Yoshida, Y.; Matsui, S.; Fujita, T. Bis(pyrrolide-imine) Ti complexes with MAO: A new family of high performance catalysts for olefin polymerization. J. Organomet. Chem. 2005, 690, 4382-4397. doi: 10.1016/j.jorganchem.2005.01.038
46. [46]
  Tomoaki, M.; Terunori, F. High-performance olefin polymerization catalysts discovered on the basis of a new catalyst design concept. Chem. Soc. Rev. 2008, 37, 1264-1277. doi: 10.1039/b708843b
47. [47]
  Sun, Q.; Cheng, R.; Liu, Z.; He, X.; Zhao, N.; Liu, B. Effect of F-modification over Phillips Cr/SiO₂ catalyst for ethylene polymerization. ChemCatChem 2016, 9, 3364-3373.
48. [48]
  Zhang, H.; Hu, Y.; Zhang, C.; Lee, D.; Yoon, K.; Zhang, X. Electrochemically assisted ethylene (co-)polymerization with a vanadium-based Ziegler-Natta catalyst. Catal. Commun. 2016, 83, 39-42. doi: 10.1016/j.catcom.2016.04.024
49. [49]
  Adisson, E.; Deffieux, A.; Fontanille, M. Polymerization of ethylene at high temperature by vanadium-based heterogeneous Ziegler-Natta catalysts. I. Study of the deactivation process. J. Polym. Sci., Part A: Polym. Chem. 1993, 31, 831-839.
50. [50]
  Adisson, E.; Deffieux, A.; Fontanille, M.; Bujadoux, K. Polymerization of ethylene at high temperature by vanadium-based heterogeneous Ziegler-Natta catalysts. II. Study of the activation by halocarbons. J. Polym. Sci., Part A: Polym. Chem. 1994, 32, 1033-1041.
51. [51]
  Jin, Y.; Zhao, N.; Cheng, R.; He, X.; Liu, Z.; Liu, B. Remarkable promotion effect of sulfation over the SiO₂-supported vanadium-oxide‐based catalysts for UHMWPE. Macromol. Chem. Phys. 2017, 218, 1700236. doi: 10.1002/macp.v218.19
52. [52]
  Espelid, Ø.; Børve, K. J. Theoretical models of ethylene polymerization over a mononuclear chromium(II)/silica site. J. Catal. 2000, 195, 125-139. doi: 10.1006/jcat.2000.2986
53. [53]
  Liu, B.; Fang, Y.; Terano, M. High resolution X-ray photoelectron spectroscopic analysis of transformation of surface chromium species on Phillips CrO_x/SiO₂ catalysts isothermally calcined at various temperatures. J. Mol. Catal. A-Chem. 2004, 219, 165-173. doi: 10.1016/j.molcata.2004.05.001
54. [54]
  Murray, J. S.; Politzer, P. Molecular electrostatic potentials and noncovalent interactions. WIREs. Comput. Mol. Sci. 2017, 7, e1326. doi: 10.1002/wcms.1326
55. [55]
  Politzer, P.; Murray, J. S. The fundamental nature and role of the electrostatic potential in atoms and molecules. Theor. Chem. Acc. 2002, 108, 134-142. doi: 10.1007/s00214-002-0363-9
56. [56]
  Tonosaki, K.; Taniike, T.; Terano, M. Origin of broad molecular weight distribution of polyethylene produced by Phillips-type silica-supported chromium catalyst. J. Mol. Catal. A-Chem. 2011, 340, 33-38. doi: 10.1016/j.molcata.2011.03.005
57. [57]
  Hicks, J. C.; Mullis, B. A.; Jones, C. W. Sulfonic acid functionalized SBA-15 silica as a methylaluminoxane-free cocatalyst/support for ethylene polymerization. J. Am. Chem. Soc. 2007, 129, 8426-8427. doi: 10.1021/ja0727870

扫一扫看文章

计量

PDF下载量: 0
文章访问数: 2003
HTML全文浏览量: 85

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Mechanistic Study on the Dominant Promotion Effect of Al-/Ti-/Zr-modifications over the VO_x/SiO₂ UHMWPE Catalysts

通讯作者: , boping@scau.edu.cn

English

Mechanistic Study on the Dominant Promotion Effect of Al-/Ti-/Zr-modifications over the VO_x/SiO₂ UHMWPE Catalysts

Corresponding author: Bo-Ping Liu, boping@scau.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处