Cu3(BTC)2金属有机骨架复合基质膜的制备及流体催化性能

doi:10.7503/cjcu20190250

摘要/Abstract

摘要：

采用溶剂蒸发法制备了Cu₃(BTC)₂质量分数为60%的Cu₃(BTC)₂@PS复合基质膜, 并对其形貌和结构进行了表征. 结果显示, Cu₃(BTC)₂ 均匀分布于复合基质膜中且具有较好的热稳定性. 以醇醛缩醛化反应为探针反应, 测试了复合基质膜的催化性能, 结果表明, 在该膜催化下苯甲醛的转化率高达99%, 苯甲醛二乙缩醛的选择性为99%. 此类催化膜具有良好的实用性, 能实现连续24 h高效率生产苯甲醛二乙缩醛, 可将其应用于工业上的连续化生产.

关键词: 金属有机骨架, Cu₃(BTC)₂, 复合基质膜, 缩醛

Abstract:

A Cu₃(BTC)₂@PS mixed matrix membrane(MMM) with 60%(mass fraction) MOF loading was fabricated via solvent evaporation method. The catalyst was characterized by means of SEM, XRD, FTIR and TGA. The results showed that Cu₃(BTC)₂ MOF uniformly distributed on the MMM and the MMM possessed a good thermal stability. The copper of the Cu-BTC MMM served as the active sites for the flow reaction system. The as-synthesized membranes possess high surface area and excellent hydrophilicity. Cu₃(BTC)₂ MMM was evaluated as a catalyst for the aldehyde acetalization with ethanol. 99% conversion of benzaldehyde and 99% selectivity of benzaldehyde diethyl acetal was obtained, using Cu₃(BTC)₂MMM heterogeneous catalyst for 24 h. It has an excellent practicality to develop this simple mixed matrix membrane for industrial application.

Key words: Metal organic framework(MOF), Cu₃(BTC)₂, Mixed matrix membrane, Acetalization

中图分类号:

O643

TrendMD:

侯俊英, 郝建军, 王雅雅, 刘敬春. Cu₃(BTC)₂金属有机骨架复合基质膜的制备及流体催化性能. 高等学校化学学报, 2019, 40(9): 1926.

HOU Junying, HAO Jianjun, WANG Yaya, LIU Jingchun. Fabrication of Cu₃(BTC)₂ Mixed Matrix Membrane and Its Application in Continuous Flow Process ^†. Chem. J. Chinese Universities, 2019, 40(9): 1926.

图/表 8

Fig.1 SEM images of PS(A), Cu3(BTC)2(B) and Cu3(BTC)2 MMM(C)

Fig.2 XRD patterns of PS(a), Cu3(BTC)2(b) and Cu3(BTC)2 MMM(c)

Fig.3 FTIR spectra of PS(a), Cu3(BTC)2(b) and Cu3(BTC)2 MMM(c)

Fig.4 TG curves of PS(a), Cu3(BTC)2(b) and Cu3(BTC)2 MMM(c)

Fig.5 N2 adsorption-desorption isotherms and pore size distribution(inset) of Cu3(BTC)2 MMM

Table 1 Nitrogen adsorption-desorption data for Cu3(BTC)2 and Cu3(BTC)2 MMM

Sample	S_BET/ (m²·g^-1)	V_p/ (cm³·g^-1)	D_p/nm
Cu₃(BTC	1447	0.56	1.55
Cu₃(BTC)₂ MMM	79	0.12	2.35

Fig.6 Influence of alcohols on the conversion of benzaldehyde a. CH3OH; b. CH3CH2OH; c. HOCH2CH2OH.

Table 2 Acetalization of aldehydes with ethanol using different catalystsa

Entry	Catalyst	Substrate	Conversion^b(%)	Selectivity^b(%)
1	PS	Benzaldehyde
2	Cu₃(BTC)₂	Benzaldehyde	99	99
3	Cu₃(BTC)₂ MMM	Benzaldehyde	99	99
4	Cu₃(BTC)₂ MMM	p-Methoxybenzaldehyde	86	99
5	Cu₃(BTC)₂ MMM	4-Fluorobenzaldehyde	99	99
6	Cu₃(BTC)₂ MMM	Phenylacetaldehyde	99	99
7	Cu₃(BTC)₂ MMM	Furfuraldehyde	85	99
8	Cu₃(BTC)₂ MMM	1-Octaldehyde	93	99

参考文献 40

[1]	Jin F. X., Song H. Y., Kang M. R., Xia C. G., Chen J., ,J. Chem. Industry Eng., 2018,68( 12), 4471— 4485
	(金福祥, 宋河远, 康美荣, 夏春谷, 陈静.化工学报,2018,68(12), 4471— 4485)
[2]	Moghaddam F. M., Sharifi A., ,. Synth. Commun. 1995, 25, 2457— 2461
[3]	Ziarani G. M., Lashgari N., Badiei A., ,. J. Mol. Catal. Chem. 2015, 397, 166— 191
[4]	Dhakshinamoorthy A., Alvaro M., Garcia H., ,. Chem. Commun. 2012, 48, 11275— 11288
[5]	Xie R., Luo F., Zhang L., Guo S. F., Liu Z., Ju X. J., Wang W., Chu L. Y ., Small 2018, 14, 1703650
[6]	Motamedhashemi M. M. Y., Egolfopoulos F., Tsotsis T., ,. Catal. Today 2016, 268, 130— 141
[7]	Unlu D., Hilmioglu N. D., ,J. Chem. Technol. Bio., 2016, 91, 122— 130
[8]	Bet-moushoul E., Mansourpanah Y., Farhadi K., Tabatabaei M., ,. Chem. Eng. J. 2016, 283, 29— 46
[9]	Fischer K., Gawel A., Schulz P., Atanasow I., Latif A. A., Thomas I., Kuhnert M., Prager A., Griebel J., Schulze A ., Catalysts 2018, 8, 376
[10]	Yin J., Deng B. L., ,. J. Membrane Sci. 2015, 479, 256— 275
[11]	Liu Y., Zheng Y. Du B., Nasaruddin R. R., Chen T., Xie J., ,Ind. Eng. Chem. Res., 2017, 56, 2999— 3007
[12]	Wang Z., Wei Y. M., Xu Z. L., Cao Y., Dong Z. Q., Shi X. L., ,. J. Membrane Sci. 2016, 503, 69— 80
[13]	Abdullah N., Gohari R. J., Yusof N., Ismail A. F., Juhana J., Lau W. J., Matsuura T., ,Chem. Eng. J., 2016, 289, 28— 37
[14]	Baheri B., Shahverdi M., Rezakazemi M., Motaee E., Mohammadi T., ,. Chem. Eng. Commun. 2015, 202, 316— 321
[15]	Shen Y., Wang H., Zhang X., Zhang Y., ,. ACS Appl. Mater. Interfaces 2016, 8, 23371— 23378
[16]	Li P., Vermeulen N. A., Gong X., Malliakas C. D., Stoddart J. F., Hupp J. T., Farha O. K., ,. Angew. Chem. Int. Ed. 2016, 55, 10358— 10362
[17]	Shen K., Zhang L., Chen X. D., Liu L. M., Zhang D. L., Han Y., Chen J. Y., Long J. L., Luque R ., Science 2018, 359, 206— 210
[18]	Huang Y. B., Liang J., Wang X. S., Cao R., ,. Chem. Soc. Rev. 2017, 46, 126— 157
[19]	Dechnik J., Sumby C. J., Janiak C., ,Cryst. Growth Des., 2017, 17, 4467— 4488
[20]	Knebel A., Friebe S., Bigall N. C., Benzaqui M., Serre C., Caro J., ,. ACS Appl. Mater. Interfaces 2016, 8, 7536— 7544
[21]	Zhang Y. Y., Feng X., Yuan S., Zhou J. W., Wang B., ,. Inorg. Chem. Front. 2016, 3, 896— 909
[22]	Campbell J., Burgal J. D. S., Szekely G., Davies R. P., Braddock D. C., Livingston A., ,. J. Membrane. Sci. 2016, 503, 166— 176
[23]	Dechnik J., Gascon J., Doonan C J., Janiak C.,Sumby C. J ,. Angew. Chem. Int. Ed., 2017,56, 9292— 9310
[24]	Denny M. S., Moreton J. C., Benz L., Cohen S. M., ,Nat. Rev. Mater., 2016, 1, 16078
[25]	Campbell J., Davies R. P., Braddock D. C., Livingston A. G., ,. J. Mater. Chem. A 2015, 3, 9668— 9674
[26]	Friebe S., Mundstock A., Unruh D., Renz F., Caro J., ,. J. Membrane. Sci. 2016, 516, 185— 193
[27]	Yang M., Wang G., Ma H. T., ,. Chem. Commun. 2011, 47, 911— 913
[28]	Schlichte K., Kratzke T., Kaskel S., ,Micropor. Mesopor. Mat., 2004, 73, 81— 88
[29]	Hou J. Y., Luan Y., Huang X. B., Gao H. Y., Yang M., Lu Y. F., ,. New J. Chem. 2017, 41, 9123— 9129
[30]	Aroon M. A., Ismail A. F., Matsuura T., Montazer-Rahmati M. M., ,. Sep. Purif. Technol. 2010, 75, 229— 242
[31]	Bhavsar S., Patel G. B., Singh N. L., ,. Physica B: Condensed Matter 2018, 533, 12— 16
[32]	Abdelhameed R. M., Abdel-Gawad H., Elshahat M., Emam H. E., ,. RSC Adv. 2016, 6, 42324— 42333
[33]	Sorachoti K., Pangkumhang B., Tanboonchuy V., Tulaphol S., Grisdanurak N., ,. Chinese J. Chem. Eng. 2017, 25, 768— 774
[34]	Fulong C. R. P., Liu J., Pastore V. J., Lin H., Cook T. R., ,. Dalton Trans. 2014, 47, 7905— 7915
[35]	Castarlenas S., Tellez C., Cornas J., ,. J. Membrane Sci. 2017, 526, 205— 211
[36]	AbbasianM., Aali N. K., ,. J. Nanostruct. 2016, 6, 38— 45
[37]	Drenchev N., Ivanova E., Mihaylov M., Hadjiivanov K., ,. Phys. Chem. Chem. Phys. 2010, 12, 6423— 6427
[38]	DeCoste J. B., Peterson G. W., Schindler B. J., Killops K. L., ,. J. Mater. Chem. A 2013, 1, 11922— 11932
[39]	Anjum M. W., Vermoortele F., Khan A. L., Bueken B., De Vos D. E., Vankelecom I. F. J., ,. ACS Appl. Mater. Interfaces 2015, 7, 25193— 25201
[40]	Bhardwaj S. K., Sharma A., Bhardwaj N., Kukkar M., Gill A. A. S., Kim K. H., Deep A., ,. Sens. Actuators B: Chem. 2017, 240, 10— 17

Cu₃(BTC)₂金属有机骨架复合基质膜的制备及流体催化性能

Fabrication of Cu₃(BTC)₂ Mixed Matrix Membrane and Its Application in Continuous Flow Process ^†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 40

相关文章 15

编辑推荐

Metrics

本文评价

[1]	李玉龙, 谢发婷, 管燕, 刘嘉丽, 张贵群, 姚超, 杨通, 杨云慧, 胡蓉. 基于银离子与DNA相互作用的比率型电化学传感器用于银离子的检测[J]. 高等学校化学学报, 2022, 43(8): 20220202.
[2]	丁杨, 王万辉, 包明. 多孔骨架固定分子催化剂催化CO₂加氢制备甲酸研究进展[J]. 高等学校化学学报, 2022, 43(7): 20220309.
[3]	鲁聪, 李振华, 刘金露, 华佳, 李光华, 施展, 冯守华. 一种新的镧系金属有机骨架材料的合成、结构及荧光检测性质[J]. 高等学校化学学报, 2022, 43(6): 20220037.
[4]	邢珮琪, 陆通, 李光华, 王力彦. 两个镉(II)金属有机骨架的可控合成与结构相关性[J]. 高等学校化学学报, 2022, 43(10): 20220218.
[5]	李文, 乔珺一, 刘鑫垚, 刘云凌. 含萘基团的锆金属有机骨架材料对水中硝基芳烃爆炸物的荧光检测性能[J]. 高等学校化学学报, 2022, 43(1): 20210654.
[6]	赵阳洋, 刘启勇, 陈泊鑫, 赵斌, 周海梅, 李昕欣, 郑丹, 冯飞. 以金属有机骨架材料ZIF-8为固定相的硅基微气相色谱柱[J]. 高等学校化学学报, 2021, 42(6): 1736.
[7]	张仁丽, 王瑶, 遇治权, 孙志超, 王安杰, 刘颖雅. 氟改性UiO-66固载钼基过氧化物催化氧化含硫化合物[J]. 高等学校化学学报, 2021, 42(6): 1914.
[8]	李梅, 夏晓娟, 陈志雄, 杨梦, 李紫滢, 杨通, 孟爽, 杨云慧, 胡蓉. 基于铂纳米颗粒@金属有机骨架纳米模拟酶的无标记电化学赭曲霉毒素适体传感器的构建[J]. 高等学校化学学报, 2021, 42(12): 3615.
[9]	陈晓, 申博渊, 熊昊, 魏飞. 电子束敏感材料的原子尺度结构研究[J]. 高等学校化学学报, 2021, 42(1): 133.
[10]	姜笑天, 尹琦, 刘天赋, 曹荣. 金属有机骨架薄膜用于小分子和离子的高效分离[J]. 高等学校化学学报, 2020, 41(8): 1691.
[11]	谢兴钰, 赵雅香, 赵莉芝, 李日舜, 吴迪昊, 叶卉, 辛清萍, 李泓, 张玉忠. 基于金属卟啉2DMOFs仿酶催化的过氧化氢比色法检测[J]. 高等学校化学学报, 2020, 41(8): 1776.
[12]	高霞,潘会宾,乔成芳,陈凤英,周元,杨文华. 基于多级孔金属有机骨架构筑HRP固定化酶反应器及其染料降解应用[J]. 高等学校化学学报, 2020, 41(7): 1591.
[13]	王瑞, 黄新松, 刘天赋, 曹荣. 金属有机框架用于一氧化碳氧化[J]. 高等学校化学学报, 2020, 41(10): 2174.
[14]	王鹏程, 单梁, 范勇, 王莉, 徐家宁, 吴淑杰. MIL-53系列金属有机骨架化合物的合成及在Strecker反应中的催化性能[J]. 高等学校化学学报, 2019, 40(8): 1655.
[15]	李湛, 单晓雯, 杨平平, 高壮壮, 方千荣, 薛铭, 裘式纶. 新型金属有机气凝胶的合成、表征及气体吸附性能[J]. 高等学校化学学报, 2019, 40(6): 1116.