碗状双亲型ZSM-5分子筛负载金纳米粒子的制备及催化性能

doi:10.7503/cjcu20190415

摘要/Abstract

摘要：

通过不对称修饰法制备了一种碗状双亲型的ZSM-5分子筛, 其拥有一个非极性的外表面和一个可修饰的极性内表面; 进一步利用经典的氨基接枝-原位还原过程, 选择性地在其内表面生长金纳米粒子. 通过X射线粉末衍射、扫描电子显微镜、透射电子显微镜、红外光谱和X射线光电子能谱对材料进行了表征, 并考察了其催化硝基苯加氢制苯胺反应的性能. 在非常温和(室温、水作溶剂及无需氮气保护)以及更低反应物浓度(0.03 mol/L, 低于室温下硝基苯在水中的溶解度)条件下, 该催化剂展现出与其它使用有机溶剂的催化剂相当的催化活性和选择性, 而且其催化性能明显高于其它以水为溶剂的催化剂, 这表明载体的双亲型结构是提升催化性能的主要原因. 该催化剂循环使用6次后, 其催化活性和选择性仍保持在相同等级.

关键词: 金纳米粒子, ZSM-5分子筛, 不对称修饰, 选择催化, 硝基苯

Abstract:

Bowl-shaped amphiphilic ZSM-5 zeolites, which have a lipophilic outer surface and a modified hydrophilic inner surface, were prepared by asymmetric modification via a classical amino graft-in situ reduction process. The gold nanoparticles were selectively grown on the inner surface of the zeolites. The samples were characterized by means of XRD, SEM, TEM, IR and XPS, and their catalytic properties for hydrogenation of nitrobenzene to aniline were investigated. Under very mild conditions(room temperature, water as solvent, without nitrogen protection) and lower reactant concentration(0.03 mol/L, lower than the solubility of nitrobenzene in water at room temperature), the catalyst exhibited the same catalytic activity and selectivity as other catalysts using organic solvents, and was significantly higher than other catalysts using water as catalyst. The amphiphilic structure of the support was proved to be the main reason for improving the catalytic effect. After six cycles, the catalytic activity and selectivity of the catalyst remained at the same level.

Key words: Gold nanoparticles, ZSM-5 zeolite, Asymmetric modification, Selective catalysis, Nitrobenzene

中图分类号:

O613.72
O643

TrendMD:

孙思齐,王影,孙传胤,王润伟,张震东,张宗弢,裘式纶. 碗状双亲型ZSM-5分子筛负载金纳米粒子的制备及催化性能. 高等学校化学学报, 2019, 40(12): 2436.

Siqi SUN,Ying WANG,Chuanyin SUN,Runwei WANG,Zhendong ZHANG,Zongtao ZHANG,Shilun QIU. Preparation and Catalytic Performance of Bowl-shaped Amphiphilic ZSM-5 Zeolites Supported Gold Nanoparticles ^†. Chem. J. Chinese Universities, 2019, 40(12): 2436.

图/表 10

Scheme 1 Synthetic process of the samples

Fig.1 Powder XRD patterns of ZSM-5(A), etched-ZSM-5(B), E-ZSM-5(C) and Au/E-ZSM-5(D)

Fig.2 IR spectra of ZSM-5(a), lipophilic-ZSM-5(b) and etched-ZSM-5(c)

Fig.3 Carbon content of lipophilic-ZSM-5 with different silane amounts

Fig.4 SEM images of ZSM-5(A) and etched-ZSM-5 with different etching time Etching time/min: (B) 10; (C) 20; (D) 30; (E) 45; (F) 60.

Fig.5 TEM images of Au/E-ZSM-5(A), L-Au/E-ZSM-5(B) and Au/LE-ZSM-5(C)

Fig.6 Au4f XPS spectra of Au/E-ZSM-5

Fig.7 Catalytic performance of the samples

Fig.8 Schematic illustration of reduction of nitrobenzene(NB) with Au/E-ZSM-5 as catalyst

Table 1 Different conditions and catalytic performance of the samples

Catalyst(mass)	Reaction condition	Yield(%)	Selectivity(%)	Ref.
Au/E-ZSM-5(10 mg)	1 mmol NB+3 mmol NaBH₄, 25 min, 35 mL H₂O	99	100	This work
L-Au/E-ZSM-5(10 mg)	1 mmol NB+3 mmol NaBH₄, 25 min, 35 mL H₂O	2		This work
Au/ZSM-5(10 mg)	1 mmol NB+3 mmol NaBH₄, 25 min, 35 mL H₂O	20		This work
Bimetallic Au-Ag/m-SBA-15(5 mg)	0.01 mmol NB+1 mmol NaBH₄, 120 min, 10 mL EtOH	99		[10]
Ag/γ-Fe₂O₃(not mentioned)	5 mmol NB+0.5 mL hydrated hydrazine, 180 min, 10 mL EtOH, 80 ℃	70	80	[24]
C@Fe₃O₄@Pd(20 mg)	1 mmol NB+3 mmol NaBH₄, 30 min, 6 mL EtOH	99	99	[25]
Co-Ag(1:1)@NC(not mentioned)	0.5 mmol NB+2 mmol hydrated hydrazine, 60 min, 5 mL EtOH	ca. 100	100	[33]

参考文献 33

[1]	Corma A., Concepcion P., Serna P ., Angew. Chem. Int. Ed., 2007,46, 7266— 7269 doi: 10.1002/anie.200700823 URL pmid: 17579907
[2]	Jagadeesh R. V., Surkus A. E., Junge H., Pohl M. M., Radnik Ja., Rabeah J., Huan H., Schünemann V., Brückner A., Beller M ., Science, 2013,342, 1073— 1076 doi: 10.1126/science.1242642 URL
[3]	Serna P., Corma A ., ACS Catalysis, 2015,5(12), 7114— 7121 doi: 10.1021/acscatal.5b01846 URL
[4]	Liu D., Wang J., Zhang Y., Liu J., Li H., Zhou L., Wu S., Gao X ., J. Mater. Sci., 2018,53(11), 8086— 8097 doi: 10.1007/s10853-018-2085-y URL
[5]	Cárdenas-Lizana F., Gómez-Quero S., Hugon A., Delannoy L., Louis C., Keane M. A ., J. Catal., 2009,262(2), 235— 243 doi: 10.1016/j.jcat.2008.12.019 URL
[6]	Wu Q., Cheng H., Chang A., Xu W., Lu F., Wu W ., Chem. Commun., 2015,51, 16068— 16071 doi: 10.1039/c5cc06386h URL pmid: 26389826
[7]	Gund S. H., Shelkar R. S., Nagarkar J. M ., RSC Adv., 2014,4(81), 42947— 42951 doi: 10.1039/C4RA06027J URL
[8]	Liu Q., Xu Y., Qiu X., Huang C., Liu M ., J. Catal., 2019,370, 55— 60 doi: 10.1016/j.jcat.2018.12.008 URL
[9]	Kaskow I., Decyk P., Sobczak I ., Appl. Surf. Sci., 2018,444, 197— 207 doi: 10.1016/j.apsusc.2018.02.285 URL
[10]	Sareen S., Mutreja V., Pal B., Singh S ., Appl. Surf. Sci., 2018,435, 552— 562 doi: 10.1016/j.apsusc.2017.11.152 URL
[11]	Lee J., Park J. C., Song H ., Adv. Mater., 2008,20(8), 1523— 1528 doi: 10.1002/(ISSN)1521-4095 URL
[12]	Vaiano V., Iervolino G., Sannino D., Murcia J. J., Hidalgo M. C., Ciambelli P., Navío J. A ., Appl. Catal. B: Environ., 2016,188, 134— 146 doi: 10.1016/j.apcatb.2016.02.001 URL
[13]	Kotan G., Kardaş F., Yokuş Ö. A., Akyıldırım O., Saral H., Eren T., Yola M. L., Atar N ., Analytical Methods, 2016,8(2), 401— 408 doi: 10.1002/1521-3765(20020118)8:2&lt;401::AID-CHEM401&gt;3.0.CO;2-C URL pmid: 11843153
[14]	Collado L., Reynal A., Coronado J. M., Serrano D. P., Durrant J. R., De La Peña O'shea V. A ., Appl. Catal. B: Environ., 2015,178, 177— 185 doi: 10.1016/j.apcatb.2014.09.032 URL
[15]	Yang J., Mou C. Y ., Appl. Catal. B: Environ., 2018,231, 283— 291 doi: 10.1016/j.apcatb.2018.02.054 URL
[16]	Cárdenas-Lizana F., Wang X., Lamey D., Li M., Keane M .A., Kiwi-Minsker L ., Chem. Engineering J., 2014,255, 695— 704 doi: 10.1016/j.cej.2014.04.116 URL
[17]	Tsai C. H., Xu M., Kunal P., Trewyn B. G ., Catalysis Today, 2018,306, 81— 88 doi: 10.1016/j.cattod.2017.01.046 URL
[18]	Lou X. W., Yuan C., Rhoades E., Zhang Q., Archer L. A ., Adv. Funct. Mater., 2006,16(13), 1679— 1684 doi: 10.1002/(ISSN)1616-3028 URL
[19]	Liu S., Guo S., Sun S., You X. Z ., Nanoscale, 2015,7(11), 4890— 4893 doi: 10.1039/c5nr00135h URL pmid: 25697907
[20]	Zhao K., Tang H., Qiao B., Li L., Wang J ., ACS Catalysis, 2015,5(6), 3528— 3539 doi: 10.1021/cs5020496 URL
[21]	Haridas V., Sugunan S., Narayanan B. N ., J. Solid State Chemistry, 2018,262, 287— 293 doi: 10.1016/j.jssc.2018.03.037 URL
[22]	Neeli C. K. P., Puthiaraj P., Lee Y. R., Chung Y. M., Baeck S. H., Ahn W. S ., Catalysis Today, 2018,303, 227— 234 doi: 10.1016/j.cattod.2017.09.002 URL
[23]	Romanazzi G., Fiore A. M., Mali M., Rizzuti A., Leonelli C., Nacci A., Mastrorilli P., Dell’anna M. M ., Molecular Catalysis, 2018,446, 31— 38 doi: 10.1016/j.mcat.2017.12.015 URL
[24]	Zhao L. L., Wang H. F., Qi M ., Chinese J. Struct. Chem., 2016,35(6), 872— 878
[25]	Mei N., Liu B., Int. J . Hydrogen Energy, 2016,41(40), 17960— 17966 doi: 10.1016/j.ijhydene.2016.07.229 URL
[26]	Dell’anna M. M., Intini S., Romanazzi G., Rizzuti A., Leonelli C., Piccinni F., Mastrorilli P ., J. Molecular Catal. A: Chem., 2014,395, 307— 314 doi: 10.1016/j.ydbio.2014.09.005 URL pmid: 25220152
[27]	Yang S., Zhang Z. H., Chen Q., He M. Y., Wang L ., Appl. Organomet. Chem., 2017,32, e4132 doi: 10.1002/aoc.v32.3 URL
[28]	Jawale D., Gravel E., Boudet C., Shah N., Geertsen V., Li H., Namboothiri I., Doris E ., Chem. Commun., 2015,51, 1739— 1742 doi: 10.1039/C4CC09192B URL
[29]	Wang Y., Sun C. Y., Wang R. W., Zhang Z. D., Zhang D. M., Zhang Z. T., Qiu S. L ., Chem. J. Chinese Universities, 2019,40(6), 1265— 1270
	( 王影, 孙传胤, 王润伟, 张震东, 张大明, 张宗弢, 裘式纶 . 高等学校化学学报, 2019,40(6), 1265— 1270)
[30]	Al-Dughaither A. S., De Lasa H ., Industrial & Engineering Chemistry Research, 2014,53(40), 15303— 15316 doi: 10.1016/j.socscimed.2019.112710 URL pmid: 31829531
[31]	Kuo C. H., Huang M. H ., Langmuir, 2005,21(5), 2012— 2016 doi: 10.1021/la0476332 URL pmid: 15723503
[32]	Casaletto M. P., Longo A., Martorana A., Prestianni A., Venezia A. M ., Surf. Interface Anal., 2006,38(4), 215— 218 doi: 10.1002/(ISSN)1096-9918 URL
[33]	Zhang W., Wu W., Long Y., Wang F., Ma J ., J. Colloid Interface Sci., 2018,522, 217— 227 doi: 10.1016/j.jcis.2018.03.059 URL pmid: 29601963