CN106732818B - 基于二氧化钛的双层中空材料及其制备方法与在硫化氢光催化处理中的应用 - Google Patents
基于二氧化钛的双层中空材料及其制备方法与在硫化氢光催化处理中的应用 Download PDFInfo
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- CN106732818B CN106732818B CN201611239594.7A CN201611239594A CN106732818B CN 106732818 B CN106732818 B CN 106732818B CN 201611239594 A CN201611239594 A CN 201611239594A CN 106732818 B CN106732818 B CN 106732818B
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- titanium dioxide
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- double layer
- carboxylated
- hollow material
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 57
- 239000011796 hollow space material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title abstract description 26
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title abstract description 26
- 238000007146 photocatalysis Methods 0.000 title abstract description 14
- 230000001699 photocatalysis Effects 0.000 title abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000004793 Polystyrene Substances 0.000 claims abstract description 27
- 229920002223 polystyrene Polymers 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002077 nanosphere Substances 0.000 claims abstract description 16
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 12
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 150000002823 nitrates Chemical class 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 24
- 235000019441 ethanol Nutrition 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 229940014800 succinic anhydride Drugs 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001338 self-assembly Methods 0.000 claims description 5
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- VHKFFPOTSWQHPK-UHFFFAOYSA-N C(C)O.C1(=CC(=CC(=C1)C(=O)O)C(=O)O)C(=O)O Chemical compound C(C)O.C1(=CC(=CC(=C1)C(=O)O)C(=O)O)C(=O)O VHKFFPOTSWQHPK-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 206010013786 Dry skin Diseases 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002341 toxic gas Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000013291 MIL-100 Substances 0.000 description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
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- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Abstract
本发明公开了一种基于二氧化钛的双层中空材料及其制备方法与在硫化氢光催化处理中的应用;以粒径为180nm的聚苯乙烯纳米球为模板,以钛酸四丁酯为前驱体,煅烧制备空心二氧化钛粒子;将空心二氧化钛进行羧基化改性制备羧基化的二氧化钛;将羧基化的二氧化钛分散在乙醇中,以九水硝酸铬为组装剂、以均苯三甲酸为交联剂,进行层层自主装,制备基于二氧化钛的双层中空材料。本发明通过一系列步骤合成的TiO2@MIL‑100双层中空材料对硫化氢气体有着很好的光催化效果;并且其具有制备过程较为简便,生产原料易得等优点,在硫化氢有毒气体的处理方面具有应用前景。
Description
技术领域
本发明属于功能材料技术领域,具体涉及到一种基于二氧化钛的双层中空材料及其制备方法与在硫化氢光催化处理中的应用。
背景技术
硫化氢是一种典型的有毒气体,即使是在非常低的浓度下也会使人感到恶臭。并且当空气中硫化氢的体积分数高于10-6时,它会对人体造成相当大的伤害甚至会威胁生命健康。此外,硫化氢气体表现出相当强的酸性,当一些精密的仪器与硫化氢气体接触时,其内部精密的器件将被腐蚀导致仪器的精密度变低甚至损坏。硫化氢普遍存在于大气中,在各种行业中也会被经常使用。
二氧化钛(TiO2),可以在低浓度下来进行一些典型的有毒气体的催化氧化,其对于硫化氢气体的催化也有着显著的效果。然而,光电子-空穴对的快速重组和TiO2的窄的光响应迫使它的使用仅限于紫外光(<387纳米)。因此,二氧化钛经常以不同的方式来修饰,如掺杂过渡金属离子,与半导体的耦合等以提高光催化活性。
金属-有机骨架(MOF)是通过组装金属离子和有机配体来形成,其在药物递送、催化、气体储存和选择性吸附等方面具有显著应用;但是现有MOF材料表现出非腐蚀性气体如氢气,甲烷,二氧化碳等优异的吸附性能,而对腐蚀性硫化氢的吸附效果非常差。
发明内容
本发明目的是提供一种基于二氧化钛的双层中空材料及其制备方法,通过层层自主装法将MIL-100负载到经过改性的空心二氧化钛表面上,制备出TiO2@MIL-100双层中空材料,利用产品对硫化氢的吸附来增强二氧化钛对其的光催化效果,以实现其在硫化氢的光催化分离方面得到广泛的应用。
为了达到上述目的,本发明具体技术方案如下:
一种基于二氧化钛的双层中空材料的制备方法,包括以下步骤:
(1)以粒径为180nm的聚苯乙烯纳米球为模板,以钛酸四丁酯为前驱体,煅烧制备空心二氧化钛粒子;
(2)将空心二氧化钛进行羧基化改性制备羧基化的二氧化钛;
(3)将羧基化的二氧化钛分散在乙醇中,以九水硝酸铬为组装剂、以均苯三甲酸为交联剂,进行层层自主装,制备基于二氧化钛的双层中空材料。
上述技术方案中,步骤(1)中,氮气中,在表面活性剂存在下,将苯乙烯水溶液升温到80~90℃;然后滴入引发剂的水溶液,聚合10~20小时,制备聚苯乙烯纳米球;优选的,聚合结束后加入氯化钠得到沉淀,然后沉淀用离子交换水洗涤数次,在烘箱中干燥,得到粒径为180nm的聚苯乙烯纳米球。可以参见本发明实施例,根据本发明方法制备的聚苯乙烯纳米球粒径分布十分均匀,粒径为180nm,作为模板使用制备的中空材料大小一致,而且合适的空心尺寸可以保证中空二氧化钛的力学强度,不仅提高产品对硫化氢的处理能力,而且增加处理稳定性。
上述技术方案中,步骤(1)中,煅烧为在500~700℃煅烧2~3小时,煅烧时的升温速率为1~5℃/min;缓慢的升温速率有利于聚苯乙烯模板均匀分解而不破坏二氧化钛外壳。
上述技术方案中,步骤(1)中,将钛酸四丁酯加入乙腈中,搅拌制备钛酸四丁酯溶液;将聚苯乙烯纳米球加入溶剂中,超声分散制备聚苯乙烯悬浮液;然后将氨水、去离子水、钛酸四丁酯溶液滴入聚苯乙烯悬浮液,搅拌1小时制备混合液;然后洗涤混合液,再离心处理,得到的固体物干燥后煅烧制备空心二氧化钛粒子;钛酸四丁酯、聚苯乙烯纳米球、氨水的质量比为30:1:20。氨水抑制了钛酸四丁酯的分解使得二氧化钛外层均匀可控。
上述技术方案中,步骤(2)中,将空心二氧化钛加入硅烷偶联剂的乙醇溶液搅拌8~10小时;清洗离心之后将其转移到丁二酸酐的N,N-二甲基甲酰胺溶液中继续搅拌8~10小时;二氧化钛、硅烷偶联剂、丁二酸酐的质量比为50:1:1。
上述技术方案中,步骤(3)中,羧基化的二氧化钛、九水硝酸铬、均苯三甲酸的质量比为20:1:1;层层自组装的次数为10~20次;每次自组装的步骤为将九水硝酸铬乙醇溶液加入羧基化的二氧化钛分乙醇分散液中,搅拌,然后用乙醇清洗离心后再加入均苯三甲酸乙醇溶液,继续搅拌;然后清洗离心去除液体。层层自组装的方法使得有机金属框架材料的制备简单快速。
本发明通过苯乙烯制备聚苯乙烯作为模板,以钛酸四丁酯为前驱体,制备空心二氧化钛;然后进行羧基化改性,再通过层层自主装的方法在其表面包裹MIL-100材料,得到基于二氧化钛的双层中空材料;可以大量吸附硫化氢,实现优异的光催化效果。因此本发明公开了上述基于二氧化钛的双层中空材料在硫化氢光催化处理中的应用;同时,本发明还公开了上述基于二氧化钛的双层中空材料在污染气体处理中的应用。
本发明的优点:
1、本发明公开的基于二氧化钛的双层中空材料的制备方法采用原材料都是成本低廉,容易得到的,而且操作简便,整个过程中没有用到昂贵的设备,对工业化应用十分关键。
2、本发明公开的基于二氧化钛的双层中空材料是一种具有高表面积、高孔隙率以及具备化学可调性的新型多孔材料,对硫化氢气体具有高效率的光催化效果,可以用于各自环境下的硫化氢有毒气体的除去。
附图说明
图1 为聚苯乙烯的透射电镜图;
图2 为聚苯乙烯的扫描电镜图;
图3 为空心二氧化钛的透射电镜图;
图4 为空心二氧化钛的扫描电镜图;
图5 为TiO2@MIL-100双层中空材料的透射电镜图;
图6 为TiO2@MIL-100双层中空材料的扫描电镜图;
图7为TiO2@MIL-100双层中空材料对硫化氢气体的光催化效果曲线图。
具体实施方式
实施例一
聚苯乙烯纳米球的制备,具体步骤如下:
0.05g的十二烷基硫酸钠和15g苯乙烯单体加入到搅拌下的水80毫升,将温度在氮气保护下升温到80℃。此后,逐渐滴入20ml含0.15克过硫酸钾的水溶液。该混合物保持搅拌另外10小时,通过加入氯化钠使聚苯乙烯纳米球沉淀。最终产物用离子交换水洗涤数次,在烘箱中干燥,附图1和附图2为聚苯乙烯的TEM和SEM图,通过图片可以看出其结构分布均匀,粒径在180nm。
空心二氧化钛的制备,具体步骤如下:
0.5mL的钛酸四丁酯加入到20毫升的乙腈中,并保持搅拌10分钟。接着,0.017克的聚苯乙烯纳米球加入到90毫升的乙腈中,并通过超声分散。然后,将0.3毫升氨水,0.06毫升去离子水和20毫升钛酸四丁酯溶液滴入制备的聚苯乙烯悬浮液。将混合物在室温下搅拌1小时以完成化学反应。将产物在乙醇中洗涤,并离心三次,干燥。然后在500℃下以1℃每分钟的加热速度煅烧2小时,附图3和附图4为空心二氧化钛的TEM和SEM图,通过图片可以看出其结构分布均匀。
羧基化的二氧化钛的制备,具体步骤如下:
将空心二氧化钛加入硅烷偶联剂的乙醇溶液搅拌8小时;清洗离心之后将其转移到丁二酸酐的N,N-二甲基甲酰胺溶液中继续搅拌8小时;二氧化钛、硅烷偶联剂、丁二酸酐的质量比为50:1:1。
TiO2@MIL-100双层中空材料的制备,具体步骤如下:
将羧基化的二氧化钛分散在10毫升乙醇中,然后加入10毫升的九水硝酸铬乙醇溶液再室温下搅拌15分钟,用乙醇清洗离心后再加入10 毫升的均苯三甲酸乙醇溶液再25℃下搅拌30分钟。清洗离心后将上述程序重复20遍得到TiO2@MIL-100双层中空材料。
附图5和附图6为TiO2@MIL-100双层中空材料的TEM和SEM图,通过图片可以看出其结构。
实施例二
硫化氢气体的光催化,具体步骤如下:
将含有一个石英玻璃的间歇反应器(1.5L体积)用于硫化氢的光催化氧化。将0.5g上述制备的催化剂TiO2@MIL-100双层中空材料沉积在石英玻璃和然后将反应器抽真空。接着,1升的高纯空气和包含H2S(100 ppm的浓度)的0.5升混合气体被引入间歇式反应器, 使用GC分析H2S的浓度。
附图7为TiO2@MIL-100双层中空材料对硫化氢气体的光催化效果曲线。
通过以上分析,说明本发明通过一系列步骤合成的TiO2@MIL-100双层中空材料对硫化氢气体有着很好的光催化效果;并且其具有制备过程较为简便,生产原料易得等优点,在硫化氢有毒气体的处理方面具有应用前景。
实施例三
聚苯乙烯纳米球的制备,具体步骤如下:
0.05g的十二烷基硫酸钠和15g苯乙烯单体加入到搅拌下的水80毫升,将温度在氮气保护下升温到90℃。此后,逐渐滴入20ml含0.15克过硫酸钾的水溶液。该混合物保持搅拌另外8小时,通过加入氯化钠使聚苯乙烯纳米球沉淀。最终产物用离子交换水洗涤数次,在烘箱中干燥,可以看出其结构分布均匀,粒径在180nm。
空心二氧化钛的制备,具体步骤如下:
0.5mL的钛酸四丁酯加入到20毫升的乙腈中,并保持搅拌20分钟。接着,0.017克的聚苯乙烯纳米球加入到90毫升的乙腈中,并通过超声分散。然后,将0.3毫升氨水,0.06毫升去离子水和20毫升钛酸四丁酯溶液滴入制备的聚苯乙烯悬浮液。将混合物在室温下搅拌2小时以完成化学反应。将产物在乙醇中洗涤,并离心三次,干燥。然后在700℃下以5℃每分钟的加热速度煅烧2小时,可以看出其结构分布均匀。
羧基化的二氧化钛的制备,具体步骤如下:
将空心二氧化钛加入硅烷偶联剂的乙醇溶液搅拌10小时;清洗离心之后将其转移到丁二酸酐的N,N-二甲基甲酰胺溶液中继续搅拌10小时;二氧化钛、硅烷偶联剂、丁二酸酐的质量比为50:1:1。
TiO2@MIL-100双层中空材料的制备,具体步骤如下:
将羧基化的二氧化钛分散在10毫升乙醇中,然后加入10毫升的九水硝酸铬乙醇溶液再室温下搅拌30分钟,用乙醇清洗离心后再加入10 毫升的均苯三甲酸乙醇溶液再25℃下搅拌60分钟。清洗离心后将上述程序重复10遍得到TiO2@MIL-100双层中空材料;对硫化氢气体有着很好的光催化效果,1小时达到90%以上。
Claims (4)
1.一种基于二氧化钛的双层中空材料的制备方法,其特征在于,包括以下步骤:
(1)以粒径为180nm的聚苯乙烯纳米球为模板,以钛酸四丁酯为前驱体,煅烧制备空心二氧化钛;
(2)将空心二氧化钛进行羧基化改性制备羧基化的二氧化钛;
(3)将羧基化的二氧化钛分散在乙醇中,以九水硝酸铬为组装剂、以均苯三甲酸为交联剂,进行层层自组 装,制备基于二氧化钛的双层中空材料;
步骤(2)中,羧基化改性为将空心二氧化钛加入硅烷偶联剂的乙醇溶液中,搅拌8~10小时;然后取固体加入到丁二酸酐的N,N-二甲基甲酰胺溶液中,搅拌8~10小时得到羧基化的二氧化钛;二氧化钛、硅烷偶联剂、丁二酸酐的质量比为50:1:1;
步骤(3)中,每次自组装的步骤为将九水硝酸铬乙醇溶液加入羧基化的二氧化钛乙醇分散液中,搅拌,然后用乙醇清洗离心后再加入均苯三甲酸乙醇溶液,继续搅拌;然后清洗离心去除液体;
步骤(3)中,羧基化的二氧化钛、九水硝酸铬、均苯三甲酸的质量比为20:1:1;层层自组装的次数为10~20次。
2.根据权利要求1所述基于二氧化钛的双层中空材料的制备方法,其特征在于:步骤(1)中,氮气中,在表面活性剂存在下,将苯乙烯水溶液升温到80~90℃;然后滴入引发剂的水溶液,聚合10~20小时,聚合结束后加入氯化钠得到沉淀,然后沉淀用离子交换水洗涤,然后于60℃干燥,制备聚苯乙烯纳米球。
3.根据权利要求1所述基于二氧化钛的双层中空材料的制备方法,其特征在于:步骤(1)中,煅烧为在500~700℃煅烧2~3小时,煅烧时的升温速率为1~5℃/min。
4.根据权利要求1所述基于二氧化钛的双层中空材料的制备方法,其特征在于:步骤(1)中,将钛酸四丁酯加入乙腈中,搅拌制备钛酸四丁酯溶液;将聚苯乙烯纳米球加入溶剂中,超声分散制备聚苯乙烯悬浮液;然后将氨水、去离子水、钛酸四丁酯溶液滴入聚苯乙烯悬浮液,搅拌1小时制备混合液;然后洗涤混合液,再离心处理,得到的固体物干燥后煅烧制备空心二氧化钛粒子;钛酸四丁酯、聚苯乙烯纳米球、氨水的质量比为30:1:20。
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CN108772108B (zh) * | 2018-05-31 | 2020-12-08 | 苏州大学 | 一种可见光响应的二氧化钛纳米线/金属有机骨架/碳纳米纤维膜及其制备方法及应用 |
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