以硅藻土为硅源合成NaA分子筛及其质子传导性能研究

doi:10.7503/cjcu20200015

摘要/Abstract

摘要：

以硅藻土为硅源, 在Na₂O-Al₂O₃-SiO₂(硅藻土)-H₂O体系中, 采用水浴加热搅拌的方法在较低温度下快速合成了LTA型硅铝分子筛NaA. 通过调节温度和反应物的活性, 优化了NaA分子筛的合成过程, 实现了其在较短时间、较低温度下的快速合成. 所合成的NaA分子筛展现出良好的质子传导性能, 在室温和100%相对湿度条件下, 其质子传导率为1.72×10^-3 S/cm, 且随着温度的升高其质子传导率逐渐增大, 在80 ℃和100%相对湿度条件下, 质子传导率可以达到5.96×10^-3 S/cm.

关键词: 分子筛, 低温快速合成, 硅藻土, NaA, 质子传导

Abstract:

By utilizing diatomite as the silicon source, LTA-type silica-alumina zeolite NaA was rapid synthesized in the Na₂O-Al₂O₃-SiO₂(diatomite)-H₂O system under hydrothermal condition at low temperature. By adjusting the crystallization temperature and the activity of diatomite, the synthesis process of NaA zeolite has been further optimized, and pure phase of NaA zeolite was achieved at 70 ℃ for 3 h with stirring. The as-synthesized NaA zeolite exhibits good proton conduction property. Its proton conductivity is 1.72 10^-3 S/cm under the condition of 100%RH(Relative humidity) at room temperature. With the increase of temperature, the proton conductivity increases gradually, and the conductivity of NaA-4 reaches 5.96 10^-3 S/cm at 80 ℃ and 100%RH.

Key words: Zeolite, Low-temperature and rapid synthesis, Diatomite, NaA, Proton conduction

中图分类号:

O611.4

TrendMD:

时怀中,马文燕,张佳妮,李激扬. 以硅藻土为硅源合成NaA分子筛及其质子传导性能研究. 高等学校化学学报, 2020, 41(5): 981.

SHI Huaizhong,MA Wenyan,ZHANG Jiani,LI Jiyang. Synthesis of NaA Zeolite Using Diatomite as Silicon Source and Its Proton Conduction Property ^†. Chem. J. Chinese Universities, 2020, 41(5): 981.

图/表 5

Fig.1 SEM images(A, B) and PXRD patterns(C, D) of as-synthesized NaA-1(A, C) and NaA-2(B, D)

Fig.2 PXRD patterns(A, C) and SEM images(B, D) of the as-synthesized NaA-3(A, B) and the traditional zeolite NaA-4(C, D)

Fig.3 TGA(A) and water sorption-desorption(B) curves of NaA-3

Fig.4 Proton conductivities of NaA-3 at different temperatures(A), temperature dependence of proton conductivity of the as-synthesized NaA-3 and the proton conduction active energy Ea(B)

Fig.5 Proton conductivities of NaA-4 at different temperatures

参考文献 38

[1]	Corma A., Chem. Rev, 1997,97(6), 2373—2420 doi: 10.1021/cr960406n URL pmid: 11848903
[2]	Li J. Y., Corma A., Yu J. H., Chem. Soc. Rev., 2015,44, 7112—7127 doi: 10.1039/c5cs00023h URL pmid: 25740693
[3]	Č ejka J., Corma A., Zones S., Zeolites and Catalysis: Synthesis, Reaction and Applications, Wiley-VCH, 2010
[4]	Holm M. S., Taarning E., Egeblad K., Christensen C. H., Catal. Today, 2011,168(1), 3—16
[5]	Li J. Y., Wang B. L., Zhang H. Y., Yu J. H., Small, 2019,1805504
[6]	Chan D., Xiao Z., Guo Z., Lai Y., Zhang Y., Zhou S., Ding X., Nie H., Yang Z ., Nanoscale, 2019,11, 16968—16977 doi: 10.1039/c9nr06700k URL pmid: 31495853
[7]	Xu R. R., Pang W. Q., Huo Q. S., Yu J. H., Chen J. S., Su B. L., Qiu S. L., Yan W. F., Zeolites and Porous Materials Chemistry, Science Press, Beijing, 2014,58
	( 徐如人, 庞文琴, 霍启升, 于吉红, 陈接胜, 苏宝连, 裘式纶, 闫文付 . 分子筛与多孔材料, 北京: 科学出版社, 2014,58)
[8]	Gramich V, Meier W. M., Z. Kristallogr., 1971,133, 134—149
[9]	Reed T. B., Breck D. W., J. Am. Chem. Soc., 1956,78, 5972—5977
[10]	Kerr G. T., Inorg. Chem., 1966,5, 1537—1539
[11]	Kuehl G. H., Inorg. Chem., 1971,10, 2488—2495
[12]	Lok B. M., Messina C. A., Patton R. L., Gajek R. T., Cannan T. R., Flanigen E. M., J. Am. Chem. Soc., 1984,106, 6092—6093 doi: 10.1021/ja00332a063 URL
[13]	Simmen A., Patarin J., Baerlocher C., Proceeding of the 9^th International Zeolite Conference, Butterworth-Heinemann, Oxford, 1993, 433—440
[14]	Xu R. R., Pang W. Q., Huo Q. S., Yu J. H., Chen J. S., Su B. L., Qiu S. L., Yan W. F., Zeolites and Porous Materials Chemistry, Science Press, Beijing, 2014, 158—159
	( 徐如人, 庞文琴, 霍启升, 于吉红, 陈接胜, 苏宝连, 裘式纶, 闫文付 . 分子筛与多孔材料, 北京: 科学出版社, 2014, 158—159)
[15]	Barrer R. M., Baynham J. W., Bultitude F. W., Meier W. M., J. Chem. Soc., 1959, 195—208
[16]	Thompsom R. W., Huber M. J., J. Cryst. Gr., 1982,56(3), 711—722
[17]	Alyosef H. A., Roggendorf H., Schneider D., Inayat A., Welscher J., Schwieger W., M nster T., Kloess G., Ibrahim S., Enke D., J. Porous Mat., 2016,23, 1609—1618
[18]	Alkan M., Hopa C., Yilmaz Z., G ler H., Micropor. Mesopor. Mater., 2005,86(1—3), 176—184
[19]	Chaisena A., Rangsriwatananon K., Mater. Lett, 2005,59(12), 1474—1479
[20]	Du Y., Shi S., Dai H ., Particuology, 2011,9(2), 174—178
[21]	Ghosh B., Agrawal D. C., Bhatia S., Ind. Eng. Chem. Res., 1994,33, 2107—2110
[22]	Jia Y., Han W., Xiong G., Yang W., Mater. Lett, 2008,62(16), 2400—2403
[23]	Garcia G., Cardenas E., Cabrera S., Hedlund J., Micropor. Mesopor. Mater, 2016,219, 29—37
[24]	Yao G., Lei J., Zhang X., Sun Z., Zheng S., Komarneni S., Mater. Res. Bull, 2018,107, 132—138
[25]	Yeung K. L., Han W., Catal. Today, 2014,236, 182—205
[26]	Liang X. Q., Zhang F., Feng W., Zou X. Q., Zhao C. J., Na H., Liu C., Sun F. X., Zhu G. S., Chem. Sci., 2013,4(3), 983—992
[27]	Zhang Q., Chen H., Wu T., Jin T., Pan Z., Zheng J., Gao Y., Zhuang W., Chem. Sci, 2017,8, 1429—1435 doi: 10.1039/c6sc03320b URL pmid: 28451283
[28]	Wu G. D., Zhang H. L., Zhou J. M., Huang A. S., Wan Q., J. Mater. Chem. C, 2013,1(36), 5669—5674
[29]	Felice V., Tavares A. C., Solid State Ionics, 2011,194(1), 53—61
[30]	McKeen J. C., Yan Y. S., Davis M. E., Chem. Mater., 2008,20, 5122—5124
[31]	Mikhailenko S. D., Kaliaguine S., Ghali E., Micropor. Mat., 1997,11(1/2), 37—44
[32]	Wang N., Sun Q. M., Yan Y., Liu J. C., Yu J. H., Xu R. R., Chem. J. Chinese Universities, 2015,36(11), 2311—2316
	( 王宁, 孙启明, 颜岩, 刘健聪, 于吉红, 徐如人 . 高等学校化学学报, 2015,36(11), 2311—2316)
[33]	Mu Y., Wang Y. Y., Li Y., Li J. Y., Yu J. H., Chem. Commun., 2015,51, 2149—2151 doi: 10.1039/c4cc08964b URL pmid: 25555082
[34]	Sun Y. J., Yan Y., Wang Y. Y., Li Y., Li J. Y., Yu J. H., Chem. Commun., 2015,51, 9317—9319 doi: 10.1039/c5cc03116h URL pmid: 25960136
[35]	Zhang K., Xie X., Li H., Gao J., Nie L., Pan Y., Xie J., Tian D., Liu W., Fan Q., Su H., Huang L., Huang W., Adv. Mater, 2017,29, 1701804 doi: 10.1002/adma.v29.34 URL
[36]	Zhang F. M., Dong L. Z., Qin J. S., Guang W., Liu J., Li S. L., Lu M., Lan Y. Q., Su Z. M., Zhou H. C., J. Am. Chem. Soc., 2017,139(17), 6183—6189 doi: 10.1021/jacs.7b01559 URL pmid: 28388068
[37]	Bera S. P., Mondal A., Roy S., Dey B., Santra A., Konar S., Dalton Trans., 2018,47, 15405—15415 doi: 10.1039/c8dt03498b URL pmid: 30327814
[38]	Nascimento C. R., Sobrinho E. M. O., Assis R. B., Fagundes R. F., Bieseki L., Pergher S. B. C., Cerâmica, 2014,60, 63—68