CN108855017A - 一种三维多孔二氧化钛泡沫块体及其制备方法 - Google Patents
一种三维多孔二氧化钛泡沫块体及其制备方法 Download PDFInfo
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- CN108855017A CN108855017A CN201710322674.7A CN201710322674A CN108855017A CN 108855017 A CN108855017 A CN 108855017A CN 201710322674 A CN201710322674 A CN 201710322674A CN 108855017 A CN108855017 A CN 108855017A
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- titanium dioxide
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- porous titanium
- alkali metal
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 108
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- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 27
- 229910003087 TiOx Inorganic materials 0.000 claims abstract description 25
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- -1 alkali metal titanate Chemical class 0.000 claims abstract description 23
- 150000001412 amines Chemical class 0.000 claims abstract description 18
- 230000005588 protonation Effects 0.000 claims abstract description 16
- 150000003384 small molecules Chemical class 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 15
- 238000004108 freeze drying Methods 0.000 claims description 11
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 229920001817 Agar Polymers 0.000 claims description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008272 agar Substances 0.000 claims description 6
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
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- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000003836 solid-state method Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 2
- 239000000499 gel Substances 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 229910021645 metal ion Inorganic materials 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 6
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- 238000000746 purification Methods 0.000 abstract description 2
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- 150000002500 ions Chemical class 0.000 description 16
- 239000010936 titanium Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
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- 229910001385 heavy metal Inorganic materials 0.000 description 10
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
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- 241000894007 species Species 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000002585 base Substances 0.000 description 4
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- 239000010959 steel Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910020470 K2Ti4O9 Inorganic materials 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 230000035484 reaction time Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910020287 Na2Ti4O9 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
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- 230000006978 adaptation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 229910052804 chromium Inorganic materials 0.000 description 1
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- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
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- 238000003911 water pollution Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Abstract
本发明涉及一种三维多孔二氧化钛泡沫块体及其制备方法，包括：将质子化相层状碱金属钛酸盐置于含有小分子有机胺的溶液中，经搅拌后得到氧化钛纳米片剥离液；将所得氧化钛纳米片剥离液经过冷冻干燥，得到所述三维多孔二氧化钛泡沫块体。本发明的三维多孔二氧化钛泡沫孔径分布均匀，孔体积较大，具有十分优异的亲水性能和一定的机械强度，是金属离子吸附的合适材料，可应用于污水净化领域。
Description
技术领域
本发明涉及一种三维多孔二氧化钛泡沫块体及其制备方法和应用，具体涉及一种由氧化钛纳米片胶体制备三维多孔二氧化钛泡沫块体的方法。
背景技术
水是生命之源，为人类生活、生物生长和农业生产所必需。然而，现代工业和其它产业的发展，城市人口的增长使环境污染越来越严重，使得目前为数不多的水源遭到了大量的污染。重金属废水主要来自采矿、有色金属、电镀、电解、农药、医药、油漆、颜料等工业，主要含有镉、铬、汞、锌、铜等重金属，其种类、含量及存在形态随产生条件而异。重金属进入环境后不能被生物降解，通过食物链循环，并最终在生物体内积累，破坏生物体的正常生理代谢活动，进而危害人体健康。国内外常用的重金属废水治理方法有物理法、化学法、物理化学法、电化学法和生物法等。物理吸附法操作简单、见效快、二次污染小，是21世纪最有研究价值的处理方法之一。
但是，常用的材料如活性炭，石墨烯等，吸附性能较差，吸附速率慢，并且难以回收再利用。因此，设计和开发新材料和新工艺以应对日益严重的水污染问题具有十分重大的意义。近年来，有关无机层状化合物剥离分层制备二维单分子层纳米片(nanosheets)的研究越来越受到研究者的青睐。由层状化合物剥离生成的二维纳米片，其结构、组成与母体层状化合物板层相一致。纳米片厚度在分子尺度(1nm左右)，横向尺寸在亚微米至数微米间，表现出极端的二维各向异性。此外，剥离所得纳米片表面通常带有电荷，因此可作为基本单元用来构筑多功能复合薄膜和其它纳米复合材料。由于这些优异的物理化学性质，二维单分子层纳米片材料在能源、环境、传感和计算机芯片等领域具有十分广泛的应用前景。特别地，由于其较好的亲水性能和较高的比表面积，这种材料在重金属离子吸附方面表现出优异的性能。
但是，二维单分子层纳米片作为一种平面二维材料，片层之间十分容易堆叠，造成比表面积和孔体积大大减少，使得其直接用于吸附材料有许多困难。
发明内容
针对上述问题，本发明从从结构入手，构造适合的三维多孔二氧化钛泡沫块体，以及一种可以简单、快速制备三维多孔二氧化钛泡沫块体的制备方法。
一方面，本发明提供了一种三维多孔二氧化钛泡沫块体的制备方法，包括：
将质子化相层状碱金属钛酸盐置于含有小分子有机胺的溶液中，经搅拌后得到氧化钛纳米片剥离液；
将所得氧化钛纳米片剥离液经过冷冻干燥，得到所述三维多孔二氧化钛泡沫块体。
本发明先利用小分子有机胺对二氧化钛纳米片进行表面修饰得到氧化钛纳米片剥离液，其中高活性的氧化钛纳米片为相应的单分子片层结构。再利用冷冻干燥得到高吸附性能的二氧化钛泡沫块体。所述TiO2泡沫具有的三维互通网络的大孔结构。这种网络互通结构有着极大的比表面和互相连接的孔洞，壁墙是由再堆垛的氧化钛纳米片构成。所用剥离液的较高浓度使得纳米片之间更容易接触，在冷冻干燥的过程中，随着水的移除，氧化钛纳米片发生堆叠和自组装，形成互通连续网络结构。而这种结构由于多种相互作用力得到加强，如官能团(小分子有机胺上的氨基，水分子和氧化钛纳米片的含氧基团等)之间的范德华力和氢键作用力。
较佳地，所述冷冻干燥包括：温度：－50℃～－78℃；真空：0.5～12Pa；时间：24h～72h。
较佳地，将层状碱金属钛酸盐和浓度为0.5-2M的酸溶液按照1～40g/L的液固比混合并搅拌1-5天，每2～12小时更换一次酸溶液，得到质子化相层状碱金属钛酸盐。
又，较佳地，所述酸溶液选自可选自盐酸、硫酸和硝酸中的至少一种。
又，较佳地，选用高温固相法、水热结晶法、溶胶凝胶法中的至少一种制备层状碱金属钛酸盐。
较佳地，所述含有小分子有机胺的溶液的浓度为0.1～10mmol/L，所述含有小分子有机胺的溶液和质子化相层状碱金属钛酸盐的固液比为1～20g/L。优选地，将浓度为0.2～4mmol/L的含有小分子有机胺的溶液和质子化相层状碱金属钛酸盐按照1～10g/L的固液比混合并搅拌7～14天，得到氧化钛纳米片剥离液。
较佳地，所述小分子有机胺选自苯胺、甲胺、乙胺、丙胺和四丁基氢氧化铵中至少一种。
较佳地，将所得氧化钛纳米片剥离液和琼脂、聚乙烯醇、羧甲基纤维素钠、羧基壳聚糖中的至少一种添加剂混合后，再进行冷冻干燥，所述添加剂与质子化相层状碱金属钛酸盐的质量比为1：(20～200)。
另一方面，本发明还提供了一种根据上述方法制备的三维多孔二氧化钛泡沫块体，所述三维多孔二氧化钛泡沫块体具有三维连通的大孔结构，大孔孔径为10～100μm。
再一方面，本发明还提供了一种上述三维多孔二氧化钛泡沫块体在重金属离子吸附和光催降解有机污染物中的应用。
本发明只需冷冻干燥系统即可实现三维多孔二氧化钛泡沫块体(三维多孔二氧化钛泡沫材料)的大规模制备。本发明的三维多孔二氧化钛泡沫孔径分布均匀，孔体积较大，具有十分优异的亲水性能和一定的机械强度，是金属离子吸附的合适材料，可应用于污水净化领域。
附图说明
图1示出本发明实施例1制备得到的氧化钛纳米片剥离液实物照片，且该剥离液具有丁达尔现象，说明剥离液为胶体；
图2示出本发明实施例2制备得到的烘干之后三维多孔二氧化钛泡沫实物照片；
图3示本发明实施例3制备得到的三维多孔二氧化钛泡沫扫描电镜照片，可以观察到其中为10μm至100μm大小的孔径结构；
图4示出经本发明实施例1制备得到的三维多孔二氧化钛泡沫的高分辨透射电镜照片，从中可以看到层数大概为5层左右；
图5示出经本发明实施例2制备得到的三维多孔二氧化钛泡沫的XRD图谱，出现了一系列新的低角度衍射峰，可能来源于冷干过程中重新堆垛的氧化钛纳米片之间插入了小分子有机胺和水分子，形成层间“廊道”(d010)结构；
图6示出经本发明实施例1制备得到的三维多孔二氧化钛泡沫的接触角测试结果照片，三维多孔二氧化钛泡沫对水的接触角为0°；
图7示出经本发明实施例1制备得到的三维多孔二氧化钛泡沫吸附各种金属离子的实物照片，其中为泡沫挤压吸收液体后完全恢复到初始形状；
图8示出经本发明实施例1制备得到的三维多孔二氧化钛泡沫吸附各种金属离子的吸附动力曲线；
图9示出光催化空气净化实验装置示意图。
具体实施方式
以下通过下述实施方式进一步说明本发明，应理解，下述实施方式仅用于说明本发明，而非限制本发明。
本发明通过酸化，剥离碱金属钛酸盐，得到有机胺修饰的二氧化钛胶体，又通过简单的冷冻干燥法，得到高活性三维多孔二氧化钛泡沫块体。本发明中所述三维多孔二氧化钛泡沫，其微观形态为三维连通的大孔结构，大孔孔径在10μm～100μm之间。
本发明利用可以简单、快速的方法制备三维多孔二氧化钛泡沫。这种三维多孔二氧化钛泡沫具有优异的亲水性、较大的孔体积和一定的机械强度，因而在油污吸附方面具有较好的应用。以下示例性地说明本发明提供的三维多孔二氧化钛泡沫的制备方法。
制备层状碱金属钛酸盐。层状结构的碱金属钛酸盐(层状碱金属钛酸盐)可通过高温固相法、水热结晶法、溶胶凝胶法中的一种或几种的组合进行制备。其中层状碱金属钛酸盐粉体微观形态包括片、棒、带、管和不规则多边形中的一种或几种的组合。此外，层状碱金属钛酸盐中碱金属元素包括锂，钠，钾和铯中一种或几种的组合。所述层状结构的碱金属钛酸盐可为K2Ti4O9、CsxTi2-x/4□x/4O4(x＝0.7)(□代表Ti空位)、K0.8Ti1.73Li0.27O4等。
酸化具有层状结构的碱金属钛酸盐，得到相应的质子化相层状碱金属钛酸盐。将层状碱金属钛酸盐和浓度为0.5-2M的酸溶液按照1～40g/L的液固比混合并搅拌1-5天，每2～12小时更换一次酸溶液，得到质子化相层状碱金属钛酸盐。所述酸溶液可选自盐酸、硫酸和硝酸中的至少一种。
再利用酸碱中和原理，引入有机胺，中和层间氢离子，同时将层状钛酸盐剥离为高活性的氧化钛纳米片，并且由于有机胺的修饰，得到稳定的氧化钛纳米片剥离液(所述高活性的氧化钛纳米片为相应的单层或少层的片层结构)。具体来说，将浓度为0.1～10mmol/L的含有小分子有机胺的溶液和质子化相层状碱金属钛酸盐按照1～20g/L的固液比混合并搅拌4～14天，得到氧化钛纳米片剥离液。所述小分子有机胺可选自苯胺、甲胺、乙胺、丙胺和四丁基氢氧化铵中至少一种。其中搅拌一般在10-30℃下搅拌，优选常温(25℃)下搅拌。
通过简单的冷冻干燥法，得到高活性三维多孔二氧化钛泡沫块体。或者，还可将所得氧化钛纳米片剥离液和琼脂、聚乙烯醇、羧甲基纤维素钠、羧基壳聚糖中的至少一种添加剂混合后，再进行冷冻干燥，所述添加剂与质子化相层状碱金属钛酸盐的质量比为1：(20～200)。其中，所述冷冻干燥可包括：温度：－50℃～－78℃；真空：0.5～12Pa；时间：24h～72h。
本方法可以大规模得到二氧化钛泡沫，并且大小形状任意可调。本发明还可在二氧化钛胶体中引入催化活性物质、医学活性成份等，以使得所形成的泡沫含有活性成份分散在结构中。本发明制备得到的二氧化钛泡沫在吸附重金属离子，降解污染物，能源以及医疗等领域中有广阔的应用前景。
本发明采用ICP原子吸收光谱测得测溶液中剩余重金属离子浓度。本发明采用单轴型机械测试系统(Instron-5566，圆柱状样品高度直径比为0.3，恒定负载速度200mmmin-1)测得所述三维多孔二氧化钛泡沫块体的机械强度。
下面进一步例举实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。若无特殊说明，以下实施例中所述常温均为25℃。
实施例1：
固相烧结K2Ti4O9块体，取摩尔比K2CO3和TiO2研磨均匀，置于马弗炉中烧结，温度800摄氏度，时间20h。将得到的K2Ti4O9粉末(20g)分散于1M HCl溶液(1L)中，氢离子交换24h，中间换三次酸溶液，抽滤清洗，60℃烘干得到相应的质子化相。再利用酸碱中和原理，将10g质子化相分散于1L四丁基氢氧化铵(1mmol/L)，常温搅拌一周，得到剥离的高活性的氧化钛纳米片剥离液；通过简单的冷冻干燥法(－78℃，0.5Pa，24h)，得到高活性三维多孔二氧化钛泡沫块体；
将所得三维多孔二氧化钛泡沫块体分别放入含有200mmol/L Fe3+离子、Pb2+离子、Cu2+离子、Cr3+离子的溶液中，常温吸附，pH＝3.5，于5min，10min，20min，30min，40min，50min，60min分别测溶液中剩余离子浓度。
实施例2：
固相烧结CsxTi2-x/4□x/4O4(x＝0.7)，取Cs2CO3和TiO2(摩尔比为1：5.3)研磨均匀，置于马弗炉中烧结，温度800摄氏度，时间20h。将得到的CsxTi2-x/4□x/4O4(x＝0.7)粉末(40g)分散于2M HCl溶液(1L)中，氢离子交换12h，中间换三次酸溶液，抽滤清洗，60℃烘干得到相应的质子化相。再利用酸碱中和原理，将5g质子化相分散于1L乙胺(1mmol/L)，常温搅拌一周，得到剥离的高活性的氧化钛纳米片剥离液；通过简单的冷冻干燥法(－58℃，8Pa，36h)，得到高活性三维多孔二氧化钛泡沫块体。将所得三维多孔二氧化钛泡沫块体分别放入含有200mmol/L Fe3+离子、Pb2+离子、Cu2+离子、Cr3+离子的溶液中，常温吸附，pH＝3.5，于5min，10min，20min，30min，40min，50min，60min分别测溶液中剩余离子浓度。
实施例3：
固相烧结K0.8Ti1.73Li0.27O4，取摩尔比K2CO3，Li2CO3和TiO2研磨均匀，置于马弗炉中烧结，温度900摄氏度，时间24h。将得到的K0.8Ti1.73Li0.27O4粉末(10g)分散于0.5M HNO3溶液(1L)中，氢离子交换6h，中间换三次酸溶液，抽滤清洗，60℃烘干得到相应的质子化相。再利用酸碱中和原理，将10g质子化相分散于1L四丁基氢氧化铵(4mmol/L)，常温搅拌一周，得到剥离的高活性的氧化钛纳米片剥离液；取200mL氧化钛纳米片剥离液(6mg/L)加入5mL琼脂溶液(10g/L)搅拌均匀，通过简单的冷冻干燥法(－78℃，0.5Pa，
36h)，得到高活性三维多孔二氧化钛琼脂泡沫；
将实施例3所得高活性三维多孔二氧化钛琼脂泡沫，装入光催化柱中，进行光催降解甲醛的实验。打开紫外灯后，通入含有甲醛的空气，测量出口处甲醛浓度。光照20min后甲醛浓度即由149.5mg/m3降至6.09mg/m3，光照1h后甲醛的降解率可达到99％以上。
实施例4：
固相烧结Na2Ti4O9，取摩尔比Na2CO3和TiO2研磨均匀，置于马弗炉中烧结，温度700摄氏度，时间16h。将得到的Na2Ti4O9粉末(20g)分散于1M HCl溶液(1L)中，氢离子交换24h，中间换三次酸溶液，抽滤清洗，60摄氏度烘干得到相应的质子化相。将5g质子化相分散于1L苯胺(1mmol/L)，常温搅拌一周，得到剥离的高活性的氧化钛纳米片剥离液；取200mL氧化钛纳米片剥离液(5mg/L)加入1mL羧基壳聚糖溶液(50g/L)搅拌均匀，通过简单的冷冻干燥法(－78℃，0.5Pa，36h)，得到高活性三维多孔二氧化钛泡沫块体；
将实施例4所得高活性三维多孔二氧化钛泡沫块体，装入光催化柱中，进行光催降解甲醛的实验。打开紫外灯后，通入含有甲醛的空气，测量出口处甲醛浓度。光照30min后甲醛浓度即由142.8mg/m3降至12.09mg/m3，光照1h后甲醛的降解率可达到99％以上。
表1为本发明实施例1-4所制备的三维多孔二氧化钛泡沫块体的性能参数：
图7示出经本发明实施例1制备得到的三维多孔二氧化钛泡沫吸附各种金属离子的实物照片，其中1、2、3指的是压缩挤压排除吸附液体后，TiO2泡沫完全恢复其初始结构形状，没有任何明显结构退化和坍塌破坏；
图8示出经本发明实施例1制备得到的三维多孔二氧化钛泡沫吸附各种金属离子的吸附动力曲线，可以确定吸附达到平衡的时间，也是评估材料吸附性能的重要因素。吸附达到平衡的时间是影响重金属废水处理过程的一个重要因素，在确定的初始离子浓度(C0[Mn+]＝1mmol/L)，pH值为3.5的初始条件下，反应时间对吸附量的影响关系如图8所示。前5min内，四种金属离子的吸附速率都很快，吸附量均接近饱和吸附量的80％。随着反应时间的推移，20min后，TiO2泡沫对Fe3+的吸附最先达到吸附饱和，其它离子也在经历了40min后达到了饱和吸附。吸附完全后，溶液中重金属离子的浓度均低于10-5–10-4mmol·L-1，低于世界卫生组织(WHO)对于饮用水水质标准。
Claims (9)
1.一种三维多孔二氧化钛泡沫块体的制备方法，其特征在于，包括：
将质子化相层状碱金属钛酸盐置于含有小分子有机胺的溶液中，经搅拌后得到氧化钛纳米片剥离液；
将所得氧化钛纳米片剥离液经过冷冻干燥，得到所述三维多孔二氧化钛泡沫块体。
2.根据权利要求1所述的制备方法，其特征在于，所述冷冻干燥包括：温度：－50～－78℃；真空：0.5～12Pa；时间：24～72小时。
3.根据权利要求1或2所述的制备方法，其特征在于，将层状碱金属钛酸盐和浓度为0.5-2M的酸溶液按照1～40 g/L的液固比混合并搅拌1～5天，每2～12小时更换一次酸溶液，得到质子化相层状碱金属钛酸盐。
4.根据权利要求3所述的制备方法，其特征在于，所述酸溶液选自为盐酸、硫酸和硝酸中的至少一种。
5.根据权利要求3或4所述的制备方法，其特征在于，选用高温固相法、水热结晶法、溶胶凝胶法中的至少一种制备层状碱金属钛酸盐。
6.根据权利要求1-5中任一项所述的制备方法，其特征在于，所述含有小分子有机胺的溶液的浓度为0.1～10 mmol/L，所述含有小分子有机胺的溶液和质子化相层状碱金属钛酸盐的固液比为1～20 g/L。
7.根据权利要求1-6中任一项所述的制备方法，其特征在于，所述小分子有机胺选自苯胺、甲胺、乙胺、丙胺和四丁基氢氧化铵中至少一种。
8.根据权利要求1-7中任一项所述的制备方法，其特征在于，将所得氧化钛纳米片剥离液与琼脂、聚乙烯醇、羧甲基纤维素钠、羧基壳聚糖中的至少一种添加剂混合后，再进行冷冻干燥，所述添加剂与质子化相层状碱金属钛酸盐的质量比为1：（20～200）。
9.一种根据权利要求1-8中任一项所述方法制备的三维多孔二氧化钛泡沫块体，其特征在于，所述三维多孔二氧化钛泡沫块体具有三维连通的大孔结构，大孔孔径为10～100μm。
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| CN110156074A (zh) * | 2019-06-11 | 2019-08-23 | 山东理工大学 | 一种二氧化钛微球的制备方法 |
| CN110527105A (zh) * | 2019-08-26 | 2019-12-03 | 南京航空航天大学 | 一种超薄二维多孔金属有机框架纳米片及其制备方法 |
| CN111348676A (zh) * | 2018-12-21 | 2020-06-30 | 厦门稀土材料研究所 | 一种多孔金属氧化物纳米片及其制备方法和应用 |
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| CN110527105A (zh) * | 2019-08-26 | 2019-12-03 | 南京航空航天大学 | 一种超薄二维多孔金属有机框架纳米片及其制备方法 |
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