CN107051591B - 一种PANI/TiO2纳米复合光催化材料及制备方法 - Google Patents
一种PANI/TiO2纳米复合光催化材料及制备方法 Download PDFInfo
- Publication number
- CN107051591B CN107051591B CN201710334622.1A CN201710334622A CN107051591B CN 107051591 B CN107051591 B CN 107051591B CN 201710334622 A CN201710334622 A CN 201710334622A CN 107051591 B CN107051591 B CN 107051591B
- Authority
- CN
- China
- Prior art keywords
- tio
- pani
- solution
- photocatalytic material
- certain amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 43
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 77
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002114 nanocomposite Substances 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 27
- 239000013078 crystal Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 8
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 7
- 229940043267 rhodamine b Drugs 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 10
- 239000004408 titanium dioxide Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 239000005457 ice water Substances 0.000 description 4
- 239000004927 clay Substances 0.000 description 3
- 238000009775 high-speed stirring Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- -1 HCl Chemical class 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
本发明公开了一种PANI/TiO2纳米复合光催化材料及制备方法和应用，采用苯胺跟钛源原位反应，制备得到的TiO2和PANI两相达到分子级别的混和，不仅使TiO2对光的吸收范围拓展到可见光区域，而且有利于光生电子和空穴在两相间的输运和分离，显著增加了催化剂的光催化效率。制备得到的纳米复合光催化剂应用于罗丹明B溶液的降解，表现出优异的可见光降解性能。本发明的优点在于，聚苯胺和TiO2两相达到分子级别的混合，界面接触面积大，结合紧密，有利于光生电子‑空穴在两相间的输运和分离；制备流程简单，操作方便，不需要引入其他反应物，也无其他副产物生成，得到的纳米复合材料光催化性能优异。
Description
技术领域
本发明属于纳米复合材料领域，尤其涉及一种PANI/TiO2纳米复合光催化材料及制备方法。
背景技术
已有研究成果表明TiO2因其高效、价廉、无毒、化学性质稳定、成本低等优点，受到研究者们广泛的重视。由于TiO2光催化剂降解有毒物质和化学污染物不会产生二次污染、也无任何毒副作用，因而与传统的生物降解方法相比，使用TiO2光催化剂降解有机污染物，便成为一种更为理想而有效的方法。Mattews 在1986年和1987年，用TiO2/UV光催化法对水中含有的34种有机污染物进行了研究，发现他们的最终产物是CO2和HCl等无机小分子，这更进一步说明，TiO2光催化剂在降解有机污染物方面确实有传统方法所不能比拟的优势。除此之外，TiO2光催化剂在污水处理、空气净化、消毒抗菌、水的净化，以及癌症治疗等领域中都得到了广泛的研究和应用。
但TiO2光催化剂带隙较宽，只能被波长较短的紫外光激发，而这部分光只占太阳光的4%-6%，降低了对太阳光的利用率，因此如何高效地利用太阳光成为了人们研究的重点。目前，研究者们已经采用多种手段对TiO2进行改性，包括半导体复合、非金属掺杂、金属掺杂、表面敏化等方法。其中采用导电聚合物进行表面敏化处理已有较多研究报道。CN104857995A提供一种纳米结构的聚苯胺（PANI）修饰的N掺杂二氧化钛复合光催化剂的制备方法，该催化剂使用尿素提供N元素，形成N掺杂，有效减小了TiO2带隙宽度使吸收谱红移，从而提高了可见光光催化效率，再通过PANI修饰改性，同时实现二氧化钛光催化量子效率提高和增强可见光吸收的作用。CN105817269A提供一种炭化聚苯胺/二氧化钛复合光催化剂的制备方法，先采用溶胀法在单分散的聚苯乙烯微球表面包裹一层聚苯胺，接着利用钛酸四丁酯的水解继续包覆一层二氧化钛，最后高温烧结除去聚苯乙烯内核，得到炭化聚苯胺/二氧化钛复合光催化剂。CN102389836A提供了一种聚苯胺/二氧化钛/粘土纳米复合光催化剂及其制备方法，以四氯化钛和粘土为原料，采用原位合成法制备纳米二氧化钛/粘土复合材料，利用四氯化钛水解生成的盐酸提供苯胺聚合所需酸性环境，合成聚苯胺导电聚合物负载在二氧化钛表面，利用导电聚苯胺接受二氧化钛受光子激发产生的电子，抑制电子-空穴对复合，提高复合材料光催化性能。CN104383966A提供了三维有序大孔聚苯胺/二氧化钛复合光催化材料的制备方法。这些报道验证了聚苯胺改性TiO2的可行性及其作用机制，但这些复合材料制备大多是通过在TiO2表面进行苯胺的聚合，得到的复合材料中两相结合不紧密、接触界面面积较小。
发明内容
本发明的目的在于提供一种分子级别混合的PANI/TiO2纳米复合材料，两者通过氧化还原反应同时生成，两相结合紧密、接触界面面积大，有利于光生电子-空穴的输运和分离，不仅扩展了光响应范围，也提高了光量子传输效率，从而提高光催化效率。
本发明的另一目的在于提供一种原料便宜、工艺简单、操作方便、产品光催化性能优异的PANI/TiO2纳米复合光催化剂制备方法。
本发明通过如下技术方案实现的：首先制备过氧化钛配合物（Peroxo TitaniumComplex，缩写为PTC）水溶液，加入苯胺跟PTC发生氧化还原反应，然后加热回流，生成PANI/TiO2纳米复合材料。高分辨透镜显示PANI/TiO2纳米复合材料主要由细小的晶粒组成，晶粒尺寸为5-20 nm，晶粒的晶格间距为0.35 nm显示其为锐钛矿相TiO2，大部分小晶粒聚集形成大颗粒，尺寸为50-120 nm，其间夹杂或包裹着PANI。复合材料比表面积高达170-240 m2/g，通过罗丹明B溶液降解实验来检测该催化剂的光催化性能。
具体制备方法包括以下步骤：
1）配制过氧化钛水溶液：将不同钛源滴加(溶解)到水中，滴加氨水溶液调节体系pH至7-11，得到白色沉淀。所得沉淀经过多次去离子水洗涤除去其他杂质和离子，再加入一定量的H2O2溶液，得到透明的橙黄色溶液，室温下静置6-36 h至剩余的H2O2完全分解，即得到过氧化钛（PTC）水溶液；
2）制备PANI/TiO2复合光催化剂：在PTC水溶液中加入一定量水，稀释成0.01-1.8mol/L的PTC水溶液。在60-120 r/min搅拌，下加入无机酸水溶液调节体系pH至1-7，再加入一定量苯胺单体（苯胺/TiO2质量比为0.01%-25%），在200-400 r/min搅拌下反应6-36 h；再经过12-48 h加热回流，离心洗涤，冷冻干燥后得到PANI/TiO2纳米复合光催化剂。
所述钛源包括：钛酸四丁酯、钛酸四乙酯、钛酸四异丙酯、四氯化钛、硫酸氧钛等。
所述的无机酸包括盐酸、硫酸、磷酸、硝酸等。
本发明的有益效果是：由于采用上述技术方案，该方法利用PTC和苯胺之间的氧化还原反应，一步制备了PANI/TiO2纳米复合光催化剂，不需要引入其他氧化剂和还原剂，制备流程简单，操作方便，也无其他副产物生成；得到的PANI/TiO2纳米复合光催化剂TiO2结晶度高、晶粒小，PANI和TiO2两相达到分子级别混和，界面面积大，结合紧密，不仅扩展了TiO2的光响应范围，还有利于光生电子-空穴在两相间的输运和分离，大大提升了材料的光催化性能。
附图说明：
图1为本发明实施案例1得到的PANI/TiO2光催化材料的透射电镜图。
图2为本发明实施案例3得到的PANI/TiO2光催化材料的高分辨透射电镜图。
图3为本发明实施案例5得到的PANI/TiO2光催化材料的高分辨透射电镜图。
具体实施方式：
为了让本发明特点和优势更加明显，下面结合具体的实施案例对本发明的技术方案做进一步说明。
实施案例1
将TiCl4滴加至冰水中，得到Ti4+的无色透明溶液，滴加氨水溶液调节体系pH为8，得到白色沉淀。所得沉淀经过多次洗涤直到无法检测出氯离子，再加入一定量的H2O2溶液，得到透明的橙黄色溶液，室温下静置12 h至反应剩余的H2O2完全分解，即得过氧化钛（PTC）水溶液。加入一定量水，调节PTC浓度为 [Ti] = 0.25 mol/L。在80 r/min搅拌下,加入H2SO4溶液调节体系pH为1，加入一定量苯胺（质量比ANI/TiO2 = 5%），在400 r/min搅拌下反应24h；再经过24 h加热回流后取产物离心洗涤，冷冻干燥后得到PANI/TiO2纳米复合材料。所得的复合材料尺寸为50-80 nm，由TiO2锐钛矿晶粒包裹聚苯胺组成，平均晶粒为6 nm，如图1。
取20 mg所制备的催化剂，加入到100 mL的5 mg/L罗丹明B溶液中，在黑暗中搅拌40 min之后，在可见光（λ > 420 nm）下照射120 min，光催化的降解率为66%。
实施案例2
将钛酸四丁酯滴加至冰水中，滴加氨水溶液调节体系pH为10，得到白色沉淀。所得沉淀经过多次洗涤，再加入一定量的H2O2溶液，得到透明的橙黄色溶液，室温下静置24 h至反应剩余的H2O2完全分解，即得过氧化钛（PTC）水溶液。加入一定量水，调节PTC浓度为 [Ti]= 0.05 mol/L。在100 r/min搅拌下加入HCl溶液调节pH为4，加入一定量苯胺（质量比AN/Ti= 3%），在350 r/min搅拌下反应24 h；再经过48 h加热回流后取产物离心洗涤，冷冻干燥后得到PANI/TiO2纳米复合物。所得的复合材料呈颗粒状，尺寸为60-100 nm，由TiO2锐钛矿晶粒包裹聚苯胺组成，平均晶粒为8 nm。
取20 mg所制备的催化剂，加入到100 mL的5 mg/L罗丹明B溶液中，在黑暗中搅拌40 min之后，在可见光（λ > 420 nm）下照射120 min，光催化的降解率为70%。
实施案例3
将钛酸四乙酯滴加至冰水中，滴加氨水溶液调节体系pH为9，得到白色沉淀。所得沉淀经过多次洗涤，再加入一定量的H2O2溶液，得到透明的橙黄色溶液，室温下静置24 h至反应剩余的H2O2完全分解，即得过氧化钛（PTC）水溶液。加入一定量水，调节PTC浓度为 [Ti]= 1.2 mol/L。在120 r/min搅拌下加入HNO3溶液调节pH为6，加入一定量苯胺（质量比AN/Ti= 1%），在300 r/min高速搅拌下反应36 h；再经过48 h加热回流后取产物离心洗涤，冷冻干燥后得到PANI/TiO2纳米复合物。所得的复合材料呈叶片状，尺寸为80-120 nm，由TiO2锐钛矿晶粒包裹聚苯胺组成，平均晶粒为12 nm，如图2。
取20 mg所制备的催化剂，加入到100 mL的5 mg/L罗丹明B溶液中，在黑暗中搅拌40 min之后，在可见光（λ > 420 nm）下照射120 min，光催化的降解率为72%。
实施案例4
将钛酸四异丙酯滴加至冰水中，滴加氨水溶液调节体系pH为11，得到白色沉淀。所得沉淀经过多次洗涤，再加入一定量的H2O2溶液，得到透明的橙黄色溶液，室温下静置36h至反应剩余的H2O2完全分解，即得过氧化钛（PTC）水溶液。加入一定量水，调节PTC浓度为将PTC浓度为 [Ti] = 0.80 mol/L。在100 r/min搅拌下加入H2SO4溶液调节pH为2，加入一定量苯胺（质量比AN/Ti = 2%），在200 r/min高速搅拌下反应36 h；再经过36 h加热回流后取产物离心洗涤，冷冻干燥后得到PANI/TiO2纳米复合物。所得的复合材料呈球形，尺寸为50-120nm，由TiO2锐钛矿晶粒包裹聚苯胺组成，平均晶粒为16 nm。
取20 mg所制备的催化剂，加入到100 mL的5 mg/L罗丹明B溶液中，在黑暗中搅拌40 min之后，在可见光（λ > 420 nm）下照射120 min，光催化降解率为76%。
实施案例5
将硫酸氧钛溶于水中，得到Ti4+的无色透明溶液，滴加氨水溶液至pH为9时，得到白色沉淀。所得沉淀经过多次洗涤直到无法检测出硫酸根离子，再加入一定量的H2O2溶液，得到透明的橙黄色溶液，室温下静置36 h至反应剩余的H2O2完全分解，即得过氧化钛（PTC）水溶液。加入一定量水，调节PTC浓度为将PTC浓度为 [Ti] = 0.50 mol/L。在100 r/min搅拌下加入HNO3溶液调节pH为4，加入一定量苯胺（质量比AN/Ti = 2%），在300 r/min高速搅拌下反应24 h；再经过48 h加热回流后取产物离心洗涤，冷冻干燥后得到PANI/TiO2纳米复合物。所得的复合材料呈颗粒状，尺寸为60-100 nm，由TiO2锐钛矿晶粒包裹聚苯胺组成，平均晶粒为9 nm，如图3。
取20 mg所制备的催化剂，加入到100 mL的5 mg/L罗丹明B溶液中，在黑暗中搅拌40 min之后，在可见光（λ > 420 nm）下照射120 min，光催化的降解率为80%。
Claims (5)
1.一种PANI/ TiO2纳米复合光催化材料的制备工艺，其特征在于，具体包括以下步骤：
步骤1) 配制过氧化钛水溶液：将钛源滴加到水中，滴加氨水溶液调节体系pH至7-11，得到白色沉淀，所得沉淀经过多次去离子水洗涤除去其他杂质和离子，再加入一定量的H2O2溶液，得到透明的橙黄色溶液，在室温下静置6-36 h直至剩余的H2O2完全分解，即得到过氧化钛水溶液；
步骤2）制备PANI/TiO2复合光催化材料：在步骤1制备得到的过氧化钛水溶液中加入一定量水，稀释成浓度为0.01-1.8 mol/L溶液，在搅拌60-120 r/min搅拌下，加入无机酸水溶液调节体系pH至1-7，再加入一定量苯胺单体，在200-400 r/min搅拌下反应6-36 h；再经过12-48 h加热回流，离心洗涤，冷冻干燥后得到PANI/ TiO2纳米复合光催化材料，由TiO2锐钛矿晶粒包裹聚苯胺组成，晶粒尺寸为5-20 nm，大部分小晶粒聚集形成大颗粒，尺寸为50-120 nm。
2.根据权利要求1所述的工艺，其特征在于，所述苯胺/TiO2质量比为0.01%-25%。
3.根据权利要求1所述的工艺，其特征在于，所述钛源包括：钛酸四丁酯、钛酸四乙酯、钛酸四异丙酯、四氯化钛、硫酸氧钛。
4.根据权利要求1所述的工艺，其特征在于，所述的无机酸包括盐酸、硫酸、磷酸、硝酸。
5.根据权利要求1所述的工艺，其特征在于，所述制备得到的PANI/TiO2纳米复合光催化材料的比表面积高达170-240 m2/g。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710334622.1A CN107051591B (zh) | 2017-05-12 | 2017-05-12 | 一种PANI/TiO2纳米复合光催化材料及制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710334622.1A CN107051591B (zh) | 2017-05-12 | 2017-05-12 | 一种PANI/TiO2纳米复合光催化材料及制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107051591A CN107051591A (zh) | 2017-08-18 |
| CN107051591B true CN107051591B (zh) | 2020-07-03 |
Family
ID=59596410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710334622.1A Expired - Fee Related CN107051591B (zh) | 2017-05-12 | 2017-05-12 | 一种PANI/TiO2纳米复合光催化材料及制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107051591B (zh) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108479857B (zh) * | 2018-04-14 | 2021-04-27 | 扬州工业职业技术学院 | 一种离子液体修饰的聚苯胺/二氧化钛复合材料的制备方法 |
| CN108939952B (zh) * | 2018-09-28 | 2021-01-15 | 四川好鑫量子科技有限公司 | 一种油水分离用pmia超疏水纳米纤维膜及制备方法 |
| CN113634279A (zh) * | 2021-07-14 | 2021-11-12 | 浙江工业大学 | 一种油水双亲钛基Ag/TiO2@PANI光催化剂的制备及其应用 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102389836B (zh) * | 2011-09-23 | 2013-12-18 | 常州大学 | 聚苯胺/二氧化钛/粘土纳米复合光催化剂及其制备方法 |
| CN104383966A (zh) * | 2014-12-03 | 2015-03-04 | 中国石油大学(华东) | 三维有序大孔聚苯胺/二氧化钛复合光催化材料的制备方法及其应用 |
| CN104857995A (zh) * | 2015-05-21 | 2015-08-26 | 中国石油大学(华东) | 一种纳米结构的聚苯胺修饰的n掺杂二氧化钛复合光催化剂及其制备方法和应用 |
| CN105709842B (zh) * | 2016-01-22 | 2018-10-26 | 湖南大学 | 聚苯胺修饰的介孔单晶二氧化钛微球及其制备方法和应用 |
| CN105817269A (zh) * | 2016-05-06 | 2016-08-03 | 扬州大学 | 一种炭化聚苯胺/二氧化钛复合光催化剂的制备方法 |
-
2017
- 2017-05-12 CN CN201710334622.1A patent/CN107051591B/zh not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN107051591A (zh) | 2017-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kumar et al. | Wide spectral degradation of Norfloxacin by Ag@ BiPO4/BiOBr/BiFeO3 nano-assembly: elucidating the photocatalytic mechanism under different light sources | |
| Hasija et al. | Recent advances in noble metal free doped graphitic carbon nitride based nanohybrids for photocatalysis of organic contaminants in water: a review | |
| Jangid et al. | Polyaniline-TiO 2-based photocatalysts for dyes degradation | |
| Reddy et al. | Nanocarbons-supported and polymers-supported titanium dioxide nanostructures as efficient photocatalysts for remediation of contaminated wastewater and hydrogen production | |
| Kang et al. | Mesoporous SiO2-modified nanocrystalline TiO2 with high anatase thermal stability and large surface area as efficient photocatalyst | |
| Wang et al. | Photodegradation of methyl orange with PANI-modified BiOCl photocatalyst under visible light irradiation | |
| Rabanimehr et al. | Fabrication of Z-scheme Bi2WO6/CNT/TiO2 heterostructure with enhanced cephalexin photodegradation: Optimization and reaction mechanism | |
| Huang et al. | Honeycomb-like carbon nitride through supramolecular preorganization of monomers for high photocatalytic performance under visible light irradiation | |
| Hamdi et al. | Phthalocyanine/chitosan-TiO2 photocatalysts: Characterization and photocatalytic activity | |
| Jyothi et al. | Non-metal (oxygen, sulphur, nitrogen, boron and phosphorus)-doped metal oxide hybrid nanostructures as highly efficient photocatalysts for water treatment and hydrogen generation | |
| CN107051591B (zh) | 一种PANI/TiO2纳米复合光催化材料及制备方法 | |
| Tahir et al. | Photocatalytic degradation and hydrogen evolution using bismuth tungstate based nanocomposites under visible light irradiation | |
| Azami et al. | Formation of an amorphous carbon nitride/titania composite for photocatalytic degradation of RR4 dye | |
| Pi et al. | Properly aligned band structures in B-TiO2/MIL53 (Fe)/g-C3N4 ternary nanocomposite can drastically improve its photocatalytic activity for H2 evolution: Investigations based on the experimental results | |
| Hassan et al. | Recent advancement in Bi5O7I-based nanocomposites for high performance photocatalysts | |
| Pattanayak et al. | Noble metal–free doped graphitic carbon nitride (g-C3N4) for efficient photodegradation of antibiotics: progress, limitations, and future directions | |
| Wang et al. | Enhancement in the photocatalytic activity of TiO2 nanofibers hybridized with g-C3N4 via electrospinning | |
| Heshmatpour et al. | A probe into the effect of fixing the titanium dioxide by a conductive polymer and ceramic on the photocatalytic activity for degradation of organic pollutants | |
| CN112517081B (zh) | 金属锡卟啉轴向功能化二氧化钛的复合光催化剂及其制备方法 | |
| Saianand et al. | Conducting polymer based visible light photocatalytic composites for pollutant removal: Progress and prospects | |
| Ke et al. | In situ fabrication of Bi2O3/C3N4/TiO2@ C photocatalysts for visible-light photodegradation of sulfamethoxazole in water | |
| Zhang et al. | Novel La3+/Sm3+ co-doped Bi5O7I with efficient visible-light photocatalytic activity for advanced treatment of wastewater: Internal mechanism, TC degradation pathway, and toxicity analysis | |
| Vijayakumar et al. | Promoting spatial charge transfer of ZrO2 nanoparticles: embedded on layered MoS2/g-C3N4 nanocomposites for visible-light-induced photocatalytic removal of tetracycline | |
| Zhao et al. | Polyoxometalates-doped TiO 2/Ag hybrid heterojunction: removal of multiple pollutants and mechanism investigation | |
| Xing et al. | N-doped synergistic porous thin-walled g-C3N4 nanotubes for efficient tetracycline photodegradation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200703 |