磷酸铝分子筛AlPO4-5的常压快速合成及晶化过程的原位热重-质谱研究

doi:10.7503/cjcu20180013

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (5): 841.doi: 10.7503/cjcu20180013

• 研究论文: 无机化学 • 上一篇下一篇

磷酸铝分子筛AlPO4-5的常压快速合成及晶化过程的原位热重-质谱研究

郭俊辉¹, 闫文付¹(), 师唯², 徐如人¹

1. 吉林大学无机合成与制备化学国家重点实验室, 化学学院, 长春 130012
2. 南开大学先进能源材料化学教育部重点实验室, 化学学院, 天津 300071

收稿日期:2018-01-04 出版日期:2018-04-21 发布日期:2018-04-21
作者简介:
联系人简介: 闫文付, 男, 博士, 教授, 博士生导师, 主要从事无机微孔材料的晶化机理以及手性分子筛的合成与应用方面的研究. E-mail: yanw@jlu.edu.cn
基金资助:
国家自然科学基金(批准号: 21571075, 21320102001, 21621001)、国家重大研究发展计划项目(批准号: 2016YFB0701100)、高等学校学科创新引智计划项目(批准号: B17020和B12015)和吉林大学高层次科技创新团队项目资助.

Rapid Synthesis of Aluminophosphate Molecular Sieve AlPO₄-5 Under Ambient Pressure and In situ Thermogravimetric-Mass Spectroscopy Investigation of the Crystallization^†

GUO Junhui¹, YAN Wenfu^1,^*(), SHI Wei², XU Ruren¹

1. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, China
2. Key Laboratory of Advanced Energy Materials Chemistry, Ministry of Education, College of Chemistry, Nankai University, Tianjin 300071, China

Received:2018-01-04 Online:2018-04-21 Published:2018-04-21
Contact: YAN Wenfu E-mail:yanw@jlu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21571075, 21320102001, 21621001), the National Key Research and Development Program of China(No.2016YFB0701100), the “111” Project(Nos.B17020, B12015) and the Program for JLU Science and Technology Innovative Research Team, China.

摘要/Abstract

摘要：

分别以三乙胺、环己胺和四乙基氢氧化铵为结构导向剂, 二缩三乙二醇为溶剂, 研究了3种溶剂热合成体系在常压和自生压力条件下的晶化行为. 在常压加热条件下, 从分别含有三乙胺、环己胺和四乙基氢氧化铵的初始凝胶中快速晶化出了高结晶度的磷酸铝分子筛AlPO₄-5. 在自生压力加热条件下, 从相同的初始凝胶中分别晶化出了三维开放骨架磷酸铝JDF-20、二维层状磷酸铝UT-5以及含有磷酸铝分子筛AlPO₄-5的混相. 含有三乙胺的初始凝胶晶化过程的原位热重-质谱研究表明, 常压条件下磷酸铝分子筛AlPO₄-5主要在150~300 ℃之间生成. 实验表明, 自生压力会对有机胺(铵)的结构导向效应产生显著影响, 这加深了对分子筛以及开放骨架生成过程及机理的认识.

关键词: 磷酸铝, 分子筛, 常压, 自生压力, 热重-质谱

Abstract:

The crystallization behavior of the initial gels containing the structure-directing agents of triethylamine, cyclohexylamine or tetraethylammonium hydroxide under ambient pressure and autogenous pressure at elevated temperature was investigated. At 300 or 180 ℃ under ambient pressure, highly crystalline aluminophosphate molecular sieve AlPO₄-5 was rapidly crystallized from the initial gels containing triethylamine, cyclohexylamine or tetraethylammonium hydroxide. When the same initial gels were loaded into autoclaves and heated at 180 ℃ in an oven, three-dimensional open-framework aluminophosphate JDF-20, layered aluminophosphate UT-5, and a mixture containing aluminophosphate molecular sieve AlPO₄-5, were obtained, respectively. The crystallization process of the initial gel containing triethylamine under ambient pressure was investigated with in situ thermogravimetric-mass spectroscopy analysis. It was confirmed that the formation of aluminophosphate molecular sieve AlPO₄-5 under ambient pressure was mainly occurred in the stage of 150—300 ℃. We found that the pressure can significantly affect the structure-directing effect of amines. This finding greatly enhanced the understanding on the formation process and crystallization mechanism of zeolites and open-framework crystals.

Key words: Aluminophosphate, Molecular sieve, Ambient pressure, Autogenous pressure, Thermogravime-tric-mass spectroscopy

中图分类号:

O611.4

TrendMD:

郭俊辉, 闫文付, 师唯, 徐如人. 磷酸铝分子筛AlPO4-5的常压快速合成及晶化过程的原位热重-质谱研究. 高等学校化学学报, 2018, 39(5): 841.

GUO Junhui,YAN Wenfu,SHI Wei,XU Ruren. Rapid Synthesis of Aluminophosphate Molecular Sieve AlPO₄-5 Under Ambient Pressure and In situ Thermogravimetric-Mass Spectroscopy Investigation of the Crystallization^†. Chem. J. Chinese Universities, 2018, 39(5): 841.

图/表 10

Table 1 Crystallization of Al2O3-P2O5-R-TEG system under ambient pressure and autogenous pressure

Structure-directing agent	Gel composition n(Al₂O₃)∶n(P₂O₅)∶n(R)^*∶n(TEG)	Product
Structure-directing agent	Gel composition n(Al₂O₃)∶n(P₂O₅)∶n(R)^*∶n(TEG)	300 ℃, ambient pressure	180 ℃, ambient pressure	180 ℃, autogenous pressure
TEA	1∶1.8∶4.7∶18	AlPO₄-5	AlPO₄-5	JDF-20^[10]
CHA	1∶2∶4∶30	AlPO₄-5	AlPO₄-5	UT-5^[11]
TEAOH	1∶2∶1∶30	AlPO₄-5	AlPO₄-5	AlPO₄-5+Unknown phase

Fig.1 Simulated XRD patterns of AlPO4-5, JDF-20 and UT-5 and the experimental XRD patterns of the products crystallized from the initial gels containing triethylamine(A, D), cyclohexylamine(B, E) and tetraethylammonium hydroxide(C, F) heated at 300 and 180 ℃ under ambient pressure(A—C) and heated at 180℃ under autogenous pressure(D—F) (A)—(C) a. Simulated AlPO4-5; b. under ambient pressure at 180 ℃; c. under ambient pressure at 300 ℃. (D)—(F) a. under autogenous pressure at 180 ℃; b1. simulated JDF-20; b2. simulated UT-5; b3. simulated AlPO4-5.

Fig.2 XRD patterns of the products crystallized from the initial gels containing triethylamine(a), cyclohexylamine(b) and tetraethylammonium hydroxide(c) heated at 180 ℃(B) in a U-tube device(A)

Fig.3 Simulated XRD pattern of AlPO4-5(a) and the experimental XRD pattern of the product(b) crystallized from the initial gels containing triethylamine heated at 300 ℃ for 1 h under ambient pressure with a heating rate of 10 ℃/min

Fig.4 TG curves of the initial gel containing triethylamine(A), cyclohexylamine(B) and tetraethylammonium hydroxide(C)

Fig.5 XRD patterns of the products crystallized from the initial gels containing triethylamine(A), cyclohexylamine(B) and tetraethylammonium hydroxide(C) heated from room temperature(RT) to different temperatures with a heating rate of 10 ℃/min

Fig.6 Mass spectrum of the volatiles from the initial gel containing triethylamine when the temperature reached 100 ℃ The signals at m/z of 14, 16, 28 and 32 are from N, O, N2 and O2, respectively.

Fig.7 In situ mass spectra of the volatiles from the initial gel containing triethylamine heated at

Fig.8 Evolution of the intensity of the main m/z signals in the temperature range of 40—600 ℃ a. m/z=29; b. m/z=27; c. m/z=18; d. m/z=1; e. m/z=40; f. m/z=2.

Table 2 Possible formula of the fragments with m/z of 1, 2, 18, 27, 29 and 40 containing C, H, O and N

m/z	Fragment
1	H
2	H₂
18	H₂O
27	C₂H₃
29	C₂H₅ , CHO
40	C₂H₂N, C₃H₄

参考文献 40

[1]	Wilson S.T., Lok B. M., Messina C. A., Cannan T. R., Flanigen E. M.,. Am. Chem. Soc., 1982, 104(4), 1146—1147
[2]	Yan W.F., Yu J. H., Shi Z., Miao P., Wang K. X., Wang Y., Xu R. R., Micropor. Mesopor. Mater., 2001, 50, 151—158
[3]	Yan W.F., Yu J. H., Xu R. R., Zhu G. S., Xiao F. S., Han Y., Sugiyama K., Terasaki O., Chem.Mater., 2000, 12(9), 2517—2519
[4]	Bennett J.M., Richardson J. W., Pluth J. J., Smith J. V., Zeolites, 1987, 7(2), 160—162
[5]	Yu J.H., Xu R. R., Acc. Chem. Res., 2003, 36(7), 481—490
[6]	Yu J.H., Xu R. R., Chem. Soc. Rev., 2006, 35(7), 593—604
[7]	Davis M.E., Saldarriaga C., Montes C., Garces J., Crowdert C., Nature, 1988, 331(6158), 698—699
[8]	Huo Q.S., Xu R. R.,. Chem. Soc. Chem. Commun., 1992, (2), 168—169
[9]	Leech M.A., Cowley A. R., Prout K., Chippindale A. M., Chem. Mater., 1998, 10(1), 451—456
[10]	Huo Q.S., Xu R. R., Li S. G., Ma Z. G., Thomas J. M., Jones R. H., Chippindalec A. M., J. Chem. Soc., Chem. Commun., 1992, (12), 875—876
[11]	Oliver S., Kuperman A., Lough A., Ozin G.A., Chem. Commun., 1996, (15), 1761—1762
[12]	Sun Y.Y., Xu J., Wang Q., Wang C., Deng F., Xu R. R.,Yan W. F., Micropor. Mesopor. Mater., 2017, 240, 178—188
[13]	Wang A.T., Xu J., Wang C., Deng F., Xu R. R.,Yan W. F., Chem. Res. Chinese Universities, 2017, 33(4), 513—519
[14]	Hu C.Y., Yan W. F., Xu R. R., Acta Chim. Sinica, 2017, 75(7), 679—685
	胡成玉, 闫文付, 徐如人. 化学学报, 2017, 75(7), 679—685
[15]	Jegatheeswaran S., Cheng C., Cheng C., Micropor. Mesopor. Mater., 2015, 201, 24—34
[16]	Huang P., Xu J., Qi G.D., Deng F., Xu R. R., Yan W. F., Sci. Rep., 2016, 6, 22019
[17]	Wang A.T., Sun Y. Y., Xu R. R.,Yan W. F., Chem.. Chinese Universities, 2017, 38(5), 701—705
	王爱天, 孙洋洋, 徐如人, 闫文付. 高等学校化学学报, 2017, 38(5), 701—705
[18]	Ren X., Komarneni S., Roy D.M., Zeolites, 1991, 11(2), 142—148
[19]	Tian Y., Xu J., Wang Z., Deng F., Xu R.R., Yan W. F., Chem. Res. Chinese Universities, 2017, 33(6), 853—859
[20]	Wang Z., Yan W.F., Xu R. R., Chinese [J]. Inorg. Chem., 2017, 33(9), 1595—1620
	王子, 闫文付, 徐如人. 无机化学学报, 2017, 33(9), 1595—1620
[21]	Tekin R., Bac N., Warzywoda J., Sacco A., J. Cryst. Growth, 2015, 411, 45—48
[22]	Newalkar B.L., Kamath B. V., Jasra R. V., Bhat S. G. T., Zeolites, 1997, 18(4), 286—290
[23]	Wang D.H., Tian P., Fan D., Yang M., Gao B. B., Qiao Y. Y., Wang C., Liu Z. M., [J]. Colloid Interface Sci., 2015, 445, 119—126
[24]	Wang P.C., Zhao Y., Zhang H. B., Yu T., Zhang Y. H., Tang Y., RSC Adv., 2017, 7(38), 23272—23278
[25]	Moliner M., Rey F., Corma A., Angew. Chem. Int.Ed., 2013, 52(52), 13880—13889
[26]	Wang L., Xu Y.P., Wei Y., Duan J. C., Chen A. B., Wang B. C., Ma H. J., Tian Z. J., Lin L. W., [J]. Am. Chem. Soc., 2006, 128(23), 7432—7433
[27]	Camblor M.A., Mifsud A., Pérez P. J., Zeolites, 1991, 11(8), 792—797
[28]	Chen C.M., Jehng J. M., Catal. Lett., 2003, 85(1), 73—80
[29]	Lok B.M., Cannan T. R., Messina C. A., Zeolites, 1983, 3(4), 282—291
[30]	Xin L., Sun H., Xu R.R., Yan W. F., Sci. Rep., 2015, 5, 14940
[31]	Keoh S.H., Chaikittisilp W., Muraoka K., Mukti R. R., Shimojima A., Kumar P., Tsapatsis M., Okubo T., Chem. Mater., 2016, 28(24), 8997—9007
[32]	Lu H.Y., Xu J., Gao P., Yan W. F., Deng F., Xu R. R., Micropor. Mesopor. Mater., 2015, 208, 105—112
[33]	Wagner P., Nakagawa Y., Lee G.S., Davis M. E., Elomari S., Medrud R. C., Zones S. I., [J]. Am. Chem. Soc., 2000, 122(2), 263—273
[34]	Lu T.T., Gao P., Xu J., Wang Y. R., Yan W. F., Yu J. H., Deng F., Mu X. H., Xu R. R., Chinese [J]. Catal., 2015, 36(6), 889—896
[35]	Tian Y., Wang S.R., Yan W. F., Xu R. R., Wang Y. R., Mu X. H., Chem. [J]. Chinese Universities, 2015, 36(3), 428—435
	田野, 王淑荣, 闫文付, 徐如人, 王永睿, 慕旭宏. 高等学校化学学报, 2015, 36(3), 428—435
[36]	van Tendeloo L., Gobechiya E., Breynaert E., Martens J. A., Kirschhock C. E. A., Chem. Commun., 2013, 49(100), 11737—11739
[37]	Lu H.Y., Liu S., Xu J., Yan W. F., Liu Z. Q., Deng F., Xu R. R., Chinese [J]. Inorg. Chem., 2015, 31(9), 1885—1893
	卢慧英, 刘舒, 徐君, 闫文付, 刘志强, 邓风, 徐如人. 无机化学学报, 2015, 31(9), 1885—1893
[38]	Beatriz B.M., Fernando L. A., Joaquín P. P., Luis G. H., Micropor. Mesopor. Mater., 2017, 254, 211—224
[39]	Tong X.Q., Xu J., Li X., Li Y., Yan W. F., Yu J. H., Deng F., Sun H., Xu R. R., Micropor. Mesopor. Mater., 2013, 176, 112—122
[40]	Park M.B., Ahn N. H., Broach R. W., Nicholas C. P., Lewis G. J., Hong S. B., Chem. Mater., 2015, 27(5), 1574—1582

磷酸铝分子筛AlPO4-5的常压快速合成及晶化过程的原位热重-质谱研究

Rapid Synthesis of Aluminophosphate Molecular Sieve AlPO₄-5 Under Ambient Pressure and In situ Thermogravimetric-Mass Spectroscopy Investigation of the Crystallization^†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 40

相关文章 15

编辑推荐

Metrics

本文评价

[1]	姚伊婷, 吕佳敏, 余申, 刘湛, 李昱, 李小云, 苏宝连, 陈丽华. 等级孔微孔-介孔Fe₂O₃/ZSM-5中空分子筛催化材料的制备及催化苄基化性能[J]. 高等学校化学学报, 2022, 43(8): 20220090.
[2]	李志光, 齐国栋, 徐君, 邓风. Sn-Al-β分子筛酸性在葡萄糖转化反应中作用的固体NMR研究[J]. 高等学校化学学报, 2022, 43(6): 20220138.
[3]	陈玮琴, 吕佳敏, 余申, 刘湛, 李小云, 陈丽华, 苏宝连. 有机杂化介孔Beta分子筛的合成及在苯甲醇烷基化反应中的应用[J]. 高等学校化学学报, 2022, 43(6): 20220086.
[4]	李加富, 张凯, 王宁, 孙启明. 分子筛限域单原子金属催化剂的研究进展[J]. 高等学校化学学报, 2022, 43(5): 20220032.
[5]	孟祥龙, 杨歌, 郭海玲, 刘晨光, 柴永明, 王纯正, 郭永梅. 纳米分子筛的合成及硫化氢吸附性能[J]. 高等学校化学学报, 2022, 43(3): 20210687.
[6]	魏李娜, 彭莉, 朱锋, 顾鹏飞, 顾学红. 中空纤维Au-CeZr/FAU催化膜的制备及在富氢气氛CO选择性氧化反应中的应用[J]. 高等学校化学学报, 2022, 43(10): 20220175.
[7]	李海勃, 肖长发, 江龙, 黄云, 淡宜. MCM-41分子筛负载氯化铝催化丙烯酸甲酯与1-辛烯共聚[J]. 高等学校化学学报, 2021, 42(9): 2974.
[8]	李奕川, 朱国富, 王宇, 柴永明, 刘晨光, 何盛宝. 基底表面性质与前驱液化学环境对原位定向构筑钛硅分子筛膜的影响[J]. 高等学校化学学报, 2021, 42(9): 2934.
[9]	罗强强, 金少青, 孙洪敏, 杨为民. 液相酸溶液后补钛合成Ti-MWW分子筛[J]. 高等学校化学学报, 2021, 42(9): 2742.
[10]	张旭, 阙家乾, 侯月新, 吕佳敏, 刘湛, 雷坤皓, 余申, 李小云, 陈丽华, 苏宝连. 等级孔介孔-微孔TS-1分子筛单晶的合成及催化氯丙烯环氧化性能[J]. 高等学校化学学报, 2021, 42(8): 2529.
[11]	王磊, 孙毯毯, 闫娜娜, 马超, 刘晓娜, 田鹏, 郭鹏, 刘中民. 利用适用于SAPO-34的有机结构导向剂合成SSZ-13分子筛[J]. 高等学校化学学报, 2021, 42(6): 1716.
[12]	王冶, 张晓思, 孙丽婧, 李冰, 刘琳, 杨淼, 田鹏, 刘仲毅, 刘中民. 有机硅烷辅助合成特殊形貌SAPO分子筛[J]. 高等学校化学学报, 2021, 42(3): 683.
[13]	李健, 于明明, 孙源, 冯文华, 冯兆池, 吴剑峰. 水溶液pH对甲烷低温氧化制备甲醇的影响[J]. 高等学校化学学报, 2021, 42(3): 776.
[14]	王勇, 董彪, 孙娇, 董德录, 孙连坤. 基于分子筛模板的银/硅铝无定形结构复合材料的合成及光谱性质[J]. 高等学校化学学报, 2021, 42(10): 3233.
[15]	闻嘉丽, 张钧豪, 姜久兴. 超大孔分子筛, 十年再回顾[J]. 高等学校化学学报, 2021, 42(1): 101.

磷酸铝分子筛AlPO4-5的常压快速合成及晶化过程的原位热重-质谱研究

Rapid Synthesis of Aluminophosphate Molecular Sieve AlPO4-5 Under Ambient Pressure and In situ Thermogravimetric-Mass Spectroscopy Investigation of the Crystallization†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 40

相关文章 15

编辑推荐

Metrics

本文评价

Rapid Synthesis of Aluminophosphate Molecular Sieve AlPO₄-5 Under Ambient Pressure and In situ Thermogravimetric-Mass Spectroscopy Investigation of the Crystallization^†