Citation: CHANG Xiaowen, LU Tingting, WEI Yingzhen, GUO Mingyue, YAN Wenfu, XU Ruren. Influence of Carbon Chain Length on the Structure-Directing Effect of Ethylenediamine in the Synthesis of Open-Framework Aluminophosphates[J]. Chinese Journal of Applied Chemistry, ;2018, 35(9): 1138-1147. doi: 10.11944/j.issn.1000-0518.2018.09.180115 shu

Influence of Carbon Chain Length on the Structure-Directing Effect of Ethylenediamine in the Synthesis of Open-Framework Aluminophosphates

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, China

Corresponding author: YAN Wenfu, yanw@jlu.edu.cn
Received Date: 16 April 2018
Revised Date: 27 April 2018
Accepted Date: 3 May 2018

Fund Project: the National Natural Science Foundation of China 21571075Supported by the National Natural Science Foundation of China(No.21571075, No.21320102001, No.21621001), the National Key Research and Development Program of China(No.2016YFB0701100), the 111 Project(No.B17020), Program for JLU Science and Technology Innovative Research Teamthe 111 Project B17020the National Natural Science Foundation of China 21320102001the National Natural Science Foundation of China 21621001the National Key Research and Development Program of China 2016YFB0701100

Figures(4)

By heating the initial mixture with the molar ratio of n (Al₂O₃):n (P₂O₅):n (R):n (H₂O)=1:1:1:277 (R=ethylenediamine (EDA) or 1, 3-propanediamine (1, 3-DAP)) at 180℃, a highly crystalline three-dimensional anionic open-framework aluminophosphate of AlPO₄-12 or UiO-26 was obtained. The crystallization processes of both initial mixtures were investigated by X-ray diffraction analysis (XRD), elemental analysis, and pH measurement. The volume and the Hirshfeld charge on the N atom of the diprotonated EDA and 1, 3-DAP were calculated by the "atom volume and surface" module and the Dmol3 module in Materials Studio, respectively. Theoretical calculation shows that the charge on the N atom of diprotonated EDA or 1, 3-DAP is 0.073 e and 0.064 e (Hirshfeld), respectively. The corresponding charge density is 1.8573 and 1.3400 e/nm³ (Hirshfeld). The corresponding formal charge density is 25.44 and 20.94 e/nm³, respectively. The framework charge density of AlPO₄-12 and UiO-26 is -6.1 e/nm³ and -4.6 e/nm³, respectively. These results indicate that the change in the length of carbon-chain connected to the N atom in the amino group can affect the amount of charge and the charge density on it, which accordingly affects its initial structure-directing ability, resulting the crystallization product changed from AlPO₄-12 to UiO-26 with a smaller charge density.
- zeolite,
- aluminophosphate,
- structure-directing effect,
- charge,
- charge density
1. [1]
  Yu J H, Xu R R. Rational Approaches Toward the Design and Synthesis of Zeolitic Inorganic Open-Framework Materials[J]. Acc Chem Res, 2010,43(9):1195-1204. doi: 10.1021/ar900293m
2. [2]
  Xu R R, Pang W Q, Yu J H, et al. Chemistry of Zeolites and Related Porous Materials[M]. New York:John Wiley & Sons, 2009.
3. [3]
  Vermeiren W, Gilson J P. Impact of Zeolites on the Petroleum and Petrochemical Industry[J]. Top Catal, 2009,52(9):1131-1161. doi: 10.1007/s11244-009-9271-8
4. [4]
  Primo A, Garcia H. Zeolites as Catalysts in Oil Refining[J]. Chem Soc Rev, 2014,43(22):7548-7561. doi: 10.1039/C3CS60394F
5. [5]
  Kulprathipanja S. Zeolites in Industrial Separation and Catalysis[M]. Weinheim:Wiley-VCH, 2010.
6. [6]
  Jacobs P A, Michiel D, Sels B F. Will Zeolite-Based Catalysis be as Relevant in Future Biorefineries as in Crude Oil Refineries?[J]. Angew Chem Int Edit, 2014,53(33):8621-8626. doi: 10.1002/anie.201400922
7. [7]
  Cejka J, Corma A, Zones S. Zeolites and Catalysis: Synthesis, Reactions and Applications[M]. Wiley, 2010.
8. [8]
  Feng G, Cheng P, Yan W. Accelerated Crystallization of Zeolites via Hydroxyl Free Radicals[J]. Science, 2016,351(6278):1188-1191. doi: 10.1126/science.aaf1559
9. [9]
  Jiao F, Li J, Pan X. Selective Conversion of Syngas to Light Olefins[J]. Science, 2016,351(6277):1065-1068. doi: 10.1126/science.aaf1835
10. [10]
  Wilson S T, Lok B M, Messina C A. Aluminophosphate Molecular Sieves:A New Class of Microporous Crystalline Inorganic Solids[J]. J Am Chem Soc, 1982,104(4):1146-1147. doi: 10.1021/ja00368a062
11. [11]
  Murugavel R, Choudhury A, Walawalkar M G. Metal Complexes of Organophosphate Esters and Open-Framework Metal Phosphates:Synthesis, Structure, Transformations, and Applications[J]. Chem Rev, 2008,108(9):3549-3655. doi: 10.1021/cr000119q
12. [12]
  Yan W F, Yu J H, Xu R R. [Al₁₂P₁₃O₅₂]₃-[(CH₂)₆N₄H₃]³⁺:An Anionic Aluminophosphate Molecular Sieve with Brönsted Acidity[J]. Chem Mater, 2000,12(9):2517-2519. doi: 10.1021/cm000280h
13. [13]
  Zhou D, Chen L, Yu J H. Synthesis, Crystal Structure, and Solid-State NMR Spectroscopy of a New Open-Framework Aluminophosphate (NH₄)₂Al₄(PO₄)₄(HPO₄)·H₂O[J]. Inorg Chem, 2005,44(12):4391-4397. doi: 10.1021/ic048476x
14. [14]
  Yu J H, Xu R R. Rich Structure Chemistry in the Aluminophosphate Family[J]. Acc Chem Res, 2003,36(7):481-490. doi: 10.1021/ar0201557
15. [15]
  Xing H Z, Li J Y, Yan W F. Cotemplating Ionothermal Synthesis of a New Open-Framework Aluminophosphate with Unique Al/P Ratio of 6/7[J]. Chem Mater, 2008,20(13):4179-4181. doi: 10.1021/cm800701x
16. [16]
  WANG Ning, SUN Qiming, YAN Yan. Organotemplate-free Synthesis and Proton Conduction Properties of a Layered Aluminophosphate Na₄[Al₄P₄O₁₈]·H₂O[J]. Chem J Chinese Univ, 2015,36(11):2311-2316.
17. [17]
  Tong X Q, Yan W F, Yu J H. A Chiral Open-Framework Fluoroaluminophosphate with Enantiomeric Excess in the Bulk Product[J]. Chem Commun, 2013,49(96):11287-11289. doi: 10.1039/c3cc47241h
18. [18]
  LUO Wukui, YAN Guiyang, LI Shirong. Synthesis and Characterization of CuSAPO-5 Molecular Sieve for Toluene Adsorption[J]. Chinese J Inorg Chem, 2016,32(8):1370-1374.
19. [19]
  Wang X D, Huang Y J, Zhang X X. Synthesis of Hydrophilic Acid-Resistant Ge-ZSM-5 Membranes via Secondary Growth Method Using Silicalite-1 Zeolite as Seeds[J]. Chem Res Chinese Univ, 2017,33(1):12-16. doi: 10.1007/s40242-017-6198-7
20. [20]
  LIU Ning, WANG Jiqiong, CHEN Biaohua. Study of Eight Membered Ring Zeolitic Catalyst of Cu/SAPO-35 over NH₃-SCR[J]. Chem J Chinese Univ, 2016,37(10):1817-1825. doi: 10.7503/cjcu20160360
21. [21]
  Chen Y L, Feng L. Synthesis, Characterization and Control of Proportion of Polymorph C in ITQ-16 and ITQ-17 Films[J]. Chem Res Chinese Uinv, 2016,32(6):1-7.
22. [22]
  Barrer R M, Denny P J. Hydrothermal Chemistry of the Silicates.Part Ⅸ.Nitrogenous Alurninosilicates[J]. J Chem Soc, 1961:971-982. doi: 10.1039/jr9610000971
23. [23]
  Cundy C S, Cox P A. The Hydrothermal Synthesis of Zeolites:Precursors, Intermediates and Reaction Mechanism[J]. Micropor Mesopor Mater, 2005,82(1):1-78.
24. [24]
  Huang P, Xu J, Qi G D. Temperature-Dependence of the Influence of the Position-2-methyl Group on the Structure-Directing Effect of Piperazine in the Synthesis of Open-Framework Aluminophosphates[J]. Sci Rep-UK, 2016,622019. doi: 10.1038/srep22019
25. [25]
  Liu C Y, Gu W Y, Kong D J. The Significant Effects of the Alkali-Metal Cations on ZSM-5 Zeolite Synthesis:From Mechanism to Morphology[J]. Micropor Mesopor Mater, 2014,183:30-36. doi: 10.1016/j.micromeso.2013.08.037
26. [26]
  Lok B M, Cannan T R, Messina C A. The Role of Organic Molecules in Molecular Sieve Synthesis[J]. Zeolites, 1983,3(4):282-291. doi: 10.1016/0144-2449(83)90169-0
27. [27]
  LU Huiying, LIU Shu, XU Jun. Crystallization Process of Open-Framework Aluminophosphate AlPO4-12[J]. Chinese J Inorg Chem, 2015,31(9):1885-1893.
28. [28]
  Lu T T, Xu R R, Yan W F. Co-templated Synthesis of Polymorph A-Enriched Zeolite Beta[J]. Micropor Mesopor Mater, 2016,226:19-24. doi: 10.1016/j.micromeso.2015.12.025
29. [29]
  Park G T, Jo D H, Ahn N H. Synthesis and Structural Characterization of a CHA-type AlPO₄ Molecular Sieve with Penta-Coordinated Framework Aluminum Atoms[J]. Inorg Chem, 2017,56(14):8504-8512. doi: 10.1021/acs.inorgchem.7b01194
30. [30]
  TIAN Ye, WANG Shurong, YAN Wenfu. Influence of F^- on the Structure-directing Effect of Organic Amines in the Synthesis of Open-Framework Aluminophosphates[J]. Chem J Chinese Uinv, 2015,36(3):428-435.
31. [31]
  Tong M Q, Zhang D L, Fan W B. Synthesis of Chiral Polymorph A-Enriched Zeolite Beta with an Extremely Concentrated Fluoride Route[J]. Sci Rep-UK, 2015,511521. doi: 10.1038/srep11521
32. [32]
  Trinh T T, Tran K-Q, Zhang X Q. The Role of a Structure Directing Agent Tetramethylammonium Template in the Initial Steps of Silicate Oligomerization in Aqueous Solution[J]. Phys Chem Chem Phys, 2015,17(34):21810-21818. doi: 10.1039/C5CP02068A
33. [33]
  Wang G M, Li J H, Wei L. An Open-Framework Beryllium Phosphite with Extra-large 18-Ring Channels[J]. CrystEngComm, 2015,17(44):8414-8417. doi: 10.1039/C5CE01507C
34. [34]
  Xin L, Sun H, Xu R R. Origin of the Structure-Directing Effect Resulting in Identical Topological Open-Framework Materials[J]. Sci Rep-UK, 2015,514940. doi: 10.1038/srep14940
35. [35]
  Yan W F, Song X W, Xu R R. Molecular Engineering of Microporous Crystals:(Ⅰ)New Insight into the Formation Process of Open-Framework Aluminophosphates[J]. Micropor Mesopor Mater, 2009,123(1/2/3):50-62.
36. [36]
  Zhang B, Xu J, Fan F T. Molecular Engineering of Microporous Crystals:(Ⅲ)The Influence of Water Content on the Crystallization of Microporous Aluminophosphate AlPO₄-11[J]. Micropor Mesopor Mater, 2012,147(1):212-221. doi: 10.1016/j.micromeso.2011.06.018
37. [37]
  Tong X Q, Xu J, Xin L. Molecular Engineering of Microporous Crystals:(Ⅵ)Structure-Directing Effect in the Crystallization Process of Layered Aluminophosphates[J]. Micropor Mesopor Mater, 2012,164:56-66. doi: 10.1016/j.micromeso.2012.07.021
38. [38]
  Lu T T, Gao P, Xu J. Influence of Al³⁺ on Polymorph A Enrichment in the Crystallization of Beta Zeolite[J]. Chinese J Catal, 2015,36(6):889-896. doi: 10.1016/S1872-2067(14)60300-4
39. [39]
  WANG Aitian, SUN Yangyang, XU Ruren. Synthesis of a New Open-Framework Aluminophosphate and the Co-templating Effect in the Crystallization[J]. Chem J Chinese Univ, 2017,38(5):701-705.
40. [40]
  Tong M Q, Zhang D L, Zhu L K. An Elaborate Structure Investigation of the Chiral Polymorph A-Enriched Zeolite Beta[J]. CrystEngComm, 2016,18(10):1782-1789. doi: 10.1039/C6CE00043F
41. [41]
  Sun Y Y, Xu J, Wang Q. The Structure-Directing Effect of Organic Amines in the Multi-template/One-Structure Phenomenon of Microporous Crystal Synthesis[J]. Micropor Mesopor Mater, 2017,240:178-188. doi: 10.1016/j.micromeso.2016.11.025
42. [42]
  Tong X Q, Xu J, Li X. Molecular Engineering of Microporous Crystals:(Ⅶ)The Molar Ratio Dependence of the Structure-Directing Ability of Piperazine in the Crystallization of Four Aluminophosphates with Open-Frameworks[J]. Micropor Mesopor Mater, 2013,176:112-122. doi: 10.1016/j.micromeso.2013.03.045
43. [43]
  Keoh S H, Chaikittisilp W, Muraoka K. Factors Governing the Formation of Hierarchically and Sequentially Intergrown MFI Zeolites by Using Simple Diquaternary Ammonium Structure-Directing Agents[J]. Chem Mater, 2016,28(24):8997-9007. doi: 10.1021/acs.chemmater.6b03887
44. [44]
  Lu H Y, Xu J, Gao P. Molecular Engineering of Microporous Crystals:(viii)The Solvent-Dependence of the Structure-Directing Effect of Ethylenediamine in the Synthesis of Open-Framework Aluminophosphates[J]. Micropor Mesopor Mater, 2015,208:105-112. doi: 10.1016/j.micromeso.2015.01.048
45. [45]
  Tong X Q, Xu J, Wang C. The Dependence of the Structure-Directing Effect of Piperazine and the Crystallization Pathways of Open-Framework Aluminophosphates on the Local Environment of the Initial Mixture[J]. Micropor Mesopor Mater, 2014,183:108-116. doi: 10.1016/j.micromeso.2013.09.004
46. [46]
  Ikuno T, Chaikittisilp W, Liu Z D. Structure-Directing Behaviors of Tetraethylammonium Cations Toward Zeolite Beta Revealed by the Evolution of Aluminosilicate Species Formed During the Crystallization Process[J]. J Am Chem Soc, 2015,137(45):14533-14544. doi: 10.1021/jacs.5b11046
47. [47]
  HU Chengyu, YAN Wenfu, XU Ruren. Phase Transition Behavior of Zeolite Y Under Hydrothermal Conditions[J]. Acta Chim Sin, 2017,75(7):679-685.
48. [48]
  J Francis R, O'hare D. The Kinetics and Mechanisms of the Crystallisation of Microporous Materials[J]. J Chem Soc Dalton Trans, 1998(19):3133-3148. doi: 10.1039/a802330a
49. [49]
  Tong X Q, Xu J, Wang C. Molecular Engineering of Microporous Crystals:(Ⅴ)Investigation of the Structure-Directing Ability of Piperazine in Forming Two Layered Aluminophosphates[J]. Micropor Mesopor Mater, 2012,155:153-166. doi: 10.1016/j.micromeso.2012.01.032
50. [50]
  Parise J B. Aluminium Phosphate Frameworks with Clathrated Ethylenediamine:X-ray Characterization of Al₃P₃O₁₁(OH)₂·N₂C₂H₈(AlPO₄-12)[J]. J Chem Soc Chem Commun, 1984(21):1449-1450. doi: 10.1039/C39840001449
51. [51]
  Kongshaug K O, Fjellvåg H, Lillerud K P. Synthesis, Structure and Thermal Properties of a Novel 3D Aluminophosphate UiO-26[J]. Micropor Mesopor Mater, 2000,40(1):313-322.
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