水解剂氟化铵对Fe-SBA-15结构及催化性能的影响

doi:10.11962/1006-4990.2018-0562

摘要/Abstract

摘要：

通过水热法制备了Fe-SBA-15介孔材料,探究了水解剂氟化铵对介孔材料结构及对苯酚羟基化反应的影响。采用X射线衍射（XRD）、红外光谱（FT-IR）和氮气吸附-脱附等方法对介孔材料进行了表征,用苯酚羟基化反应对改性后介孔材料的催化性能进行了研究。结果表明:改性后的介孔材料具有良好的催化性能,其中氟与硅物质的量比为0.03时制备的介孔材料的催化性能更为优良,在固定反应条件下苯酚转化率达到36.82%、苯二酚选择性达到81.76%。

关键词: 水解剂, 氟化铵, Fe-SBA-15, 苯二酚, 羟基化

Abstract:

Fe-SBA-15 mesoporous materials were prepared by hydrothermal synthesis,and the effect of hydrolysis agent NH₄F on the mesoporous materials structure and catalytic hydroxylation of phenol was explored.The mesoporous materials were characterized by X-ray diffraction（XRD）,infrared spectroscopy（FT-IR） and N₂ adsorption desorption etc..The catalytic properties of modified mesoporous materials were studied by hydroxylation of phenol.The results indicated that the modified materials had good catalytic performance.When n（F^-）/n（Si）=0.03,the prepared mesoporous materials had better catalytic performance.Under the fixed reaction conditions,conversion of phenol and selectivity of dihydroxybenzene reached 36.82% and 81.76%,respectively.

Key words: hydrolysate, NH₄F, Fe-SBA-15, dihydroxybenzene, hydroxylation

中图分类号:

O643

邵艳秋,张宇婷,姜振双,刘素娟,任玉兰,王丽杰. 水解剂氟化铵对Fe-SBA-15结构及催化性能的影响[J]. 无机盐工业, 2019, 51(9): 97-101.

Shao Yanqiu,Zhang Yuting,Jiang Zhenshuang,Liu Sujuan,Ren Yulan,Wang Lijie. Effects of hydrolysate NH₄F on structure and catalytic properties of Fe-SBA-15[J]. Inorganic Chemicals Industry, 2019, 51(9): 97-101.

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参考文献 31

[1]	宗蒙, 黄英, 赵阳 . SBA-15介孔材料的改性及应用[J]. 材料导报, 2012,26(17):54-59.
[2]	代郁, 周亚松, 魏强 , 等. 铝修饰改性对SBA-15分子筛性质及催化剂性能的影响[J]. 燃料化学学报, 2013,41(12):1502-1506.
[3]	Restrepo-Garcia J R, Baldovino-Medrano V G, Giraldo S A . Improving the selectivity in hydrocracking of phenanthrene over mesoporo us Al-SBA-15 based Fe-W catalysts by enhancing mesoporosity and acidity[J]. Applied Catalysis A:General, 2016,510:98-109.
[4]	Cruz P, Pérez Y, del Hierro I ,et al.Copper,copper oxide nanoparticles and copper complexes supported on mesoporous SBA-15 as cataly sts in the selective oxidation of benzyl alcohol in aqueous phase[J]. Microporous and Mesoporous Materials, 2016,220:136-147.
[5]	Zhang J, Xin Z, Meng X , et al. Effect of MoO₃ on the heat resistant performances of nickel based MCM-41 methanation catalysts[J]. Fuel, 2014,116:25-33.
[6]	Meloni D, Perra D, Monaci R , et al. Transesterification of Jatropha curcas oil and soybean oil on Al-SBA-15 catalysts[J]. Applied Ca talysis B:Environmental, 2016,184:163-173.
[7]	裘式纶, 庞文琴, 张春田 . 弱酸性介质中Fe-ZSM-5型分子筛的合成与鉴定[J]. 无机化学学报, 1988,4(4):11-19.
[8]	Li Y, Zhang W, Zhang L , et al. Direct synjournal of Al-SBA-15 mesoporous materials via hydrolysis controlled approach[J]. Journal of Physical Chemistry B, 2004,108:9739-9744.
[9]	Zhang W H, Lu J Q, Han B , et al. Direct synjournal and characteriza tion of titanium-substituted mesoporous molecular sieve SBA-15[J]. Chemistry of Materials, 2002,14:3413-3421.
[10]	Boissiere C, Larbot A, van der Lee A ,et al.A new synjournal of meso porous MSU-X silica controlled by a two-step pathway[J]. Chemistry of Materials, 2000,12(10):2902-2913.
[11]	Li Y, Feng Z, Lian Y , et al. Direct synjournal of highly ordered Fe SBA-15 mesoporous materials under weak acidic conditions[J]. Microporous and Mesoporous Materials, 2005,84:41-49.
[12]	张涛, 冯秀娟, 颜美 , 等. SBA-15负载钯催化剂的制备及其在超临界二氧化碳介质中催化Suzuki偶联反应的研究[J]. 分子科学学报, 2008,24(1):1-5.
[13]	Zhao D, Feng J, Huo Q , et al. Triblock copolymer syntheses of meso porous silica with periodic 50 to 300 angstrom pores[J]. Science, 1998,279(5350):548-552.
[14]	王冬华 . 氧化锌/SBA-15复合材料制备及其光致发光性质[J]. 无机盐工业, 2018,50(4):27-29.
[15]	明阳, 王雷, 王俊峰 , 等. 金属改性SBA-15介孔分子筛水热稳定性研究[J]. 精细石油化工, 2017,34(3):30-35.
[16]	闫宏宇 . 介孔Fe,Al-SBA-15的制备、表征及NH₃-SCR催化性能的研究[D]. 南京:南京理工大学, 2015.
[17]	Martinez F, Han Y J, Stucky G , et al. Synjournal and characterization of iron-containing SBA-15 mesoporous silica[J]. Studies in Surface Science and Catalysis, 2002,142:1109-1116.
[18]	Gao Q, Xu W, Xu Y , et al. Amino acid adsorption on mesoporous materials:influence of types of amino acids,modification of mesoporous materials,and solution conditions[J]. Journal of Physical Chemistry B, 2008,112(7):2261-2267.
[19]	Xie W, Hu L . Biguanide-functionalized mesoporous SBA-15 silica as an efficient solid catalyst for interesterification of vegetable oils[J]. Food Chemistry, 2016,197:92-99.
[20]	徐玲, 刘建华, 郭兰兰 , 等. TiO₂-SBA-15催化剂的制备、表征及光催化降解甲基橙[J]. 分子科学学报, 2015,31(4):333-337.
[21]	Wu M, Lin G, Chen D , et al. Solhydrothermal synjournal and hydro thermally structural evolution of nanocrystal titanium dioxide[J]. Chemistry of Materials, 2002,14(5):1974-1980.
	22] Corma A . From microporous to mesoporous molecular sieve materi als and their use in catalysis22] Corma A.From microporous to mesoporous molecular sieve materi als and their use in catalysis[J]. Chemical Reviews, 1997,97(6):2373-2419.
[23]	Guidotti M, Ravasio N, Psaro R , et al. Epoxidation on titanium-cont aining silicates:do structural features really affect the catalytic performance?[J]. Journal of Catalysis, 2003,214(2):242-250.
[24]	Han Y J, Kim J M, Stucky G D . Preparation of noble metal nanowires using hexagonal mesoporous silica SBA-15[J]. Chemistry of Materials, 2000,12(8):2068-2069.
[25]	Zhao D Y, Huo Q S, Feng J L , et al. Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly ordered,hydrothermally stable,mesoporous silica structures[J]. Journal of the American Chemical Society, 1998,120:6024-6036.
[26]	李瑛 . Al-SBA-15和Fe-SBA-15介孔材料的合成、表征及催化性能研究[D]. 大连:中国科学院大连化学物理研究所, 2005.
[27]	Pachamuthu M P, Srinivasan V V, Maheswari R , et al. The impact of the copper source on the synjournal of mesostructured CuTUD-1:A promising catalyst for phenol hydroxylation[J]. Catalysis Science & Technology, 2013,3(12):3335-3342.
[28]	陶明, 刘华彦, 俞喆雷 , 等. TS-1/堇青石整体催化剂催化苯酚羟基化制苯二酚[J]. 工业催化, 2017,25(2):46-51.
[29]	Mohamed M M, Eissa N A . Characterization of intrazeolitic Fe³⁺prepared by chemical vapor deposition of [(C₅H₅)Fe(CO)₂]₂ inside NaY and FSM-16 zeolites and their catalytic activities towards phenol hydroxylation [J]. Materials Research Bulletin, 2003,38(15):1993-2007. doi: 10.1016/j.materresbull.2003.09.015
[30]	Choi J S, Yoon S S, Jang S H , et al. Phenol hydroxylation using Fe-MCM-41 catalysts[J]. Catalysis Today, 2006,111(3/4):280-287. doi: 10.1016/j.cattod.2005.10.037
[31]	张晓晓 . 高结晶度和铁含量FeAPO-5分子筛的绿色合成及其苯酚羟基化性能研究[D]. 兰州:兰州理工大学, 2018.

样品	比表面积/ （m²·g^-1）	孔体积/ （cm³·g^-1）	平均孔直径/ nm
SBA-15	880.84	1.57	7.94
Fe-SBA-15	843.44	1.14	5.39
Fe-SBA-15（0.01）	833.61	1.47	6.44
Fe-SBA-15（0.02）	783.44	1.32	6.67
Fe-SBA-15（0.03）	681.11	1.30	6.76
Fe-SBA-15（0.04）	699.96	1.47	6.82
Fe-SBA-15（0.05）	764.58	1.84	7.22

样品	[n（Fe）/n（Si）]/%		嫁接率/ %
样品	理论值	实际值	嫁接率/ %
Fe-SBA-15	5	2.37	47.4
Fe-SBA-15（0.01）	5	2.89	57.8
Fe-SBA-15（0.02）	5	3.04	60.8
Fe-SBA-15（0.03）	5	3.22	64.4
Fe-SBA-15（0.04）	5	2.51	50.2
Fe-SBA-15（0.05）	5	2.19	43.8

催化剂	苯酚转化率/%	邻苯二酚选择性/%	对苯二酚选择性/%
SBA-15	1.35	—	—
Fe-SBA-15	23.61	37.25	29.73
Fe-SBA-15（0.01）	29.56	38.76	31.75
Fe-SBA-15（0.02）	33.17	40.13	32.63
Fe-SBA-15（0.03）	36.82	45.51	36.25
Fe-SBA-15（0.04）	21.47	19.70	11.57
Fe-SBA-15（0.05）	18.10	10.55	8.14

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