CN108311142A - 一种基于二氧化钛纳米管制备Ag改性二氧化钛纳米颗粒的方法 - Google Patents
一种基于二氧化钛纳米管制备Ag改性二氧化钛纳米颗粒的方法 Download PDFInfo
- Publication number
- CN108311142A CN108311142A CN201711432084.6A CN201711432084A CN108311142A CN 108311142 A CN108311142 A CN 108311142A CN 201711432084 A CN201711432084 A CN 201711432084A CN 108311142 A CN108311142 A CN 108311142A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- nano particles
- titania nanotube
- dioxide nano
- tio
- 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.)
- Pending
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000002071 nanotube Substances 0.000 title claims abstract description 22
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 14
- 230000008021 deposition Effects 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 8
- 239000011858 nanopowder Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- ZGCHATBSUIJLRL-UHFFFAOYSA-N hydrazine sulfate Chemical class NN.OS(O)(=O)=O ZGCHATBSUIJLRL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 241000196171 Hydrodictyon reticulatum Species 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 abstract description 6
- 229940012189 methyl orange Drugs 0.000 abstract description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 3
- 230000005622 photoelectricity Effects 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 7
- OXAUNDBQHKIUSD-UHFFFAOYSA-N azanium;titanium;fluoride Chemical class [NH4+].[F-].[Ti] OXAUNDBQHKIUSD-UHFFFAOYSA-N 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical group [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 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 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种基于二氧化钛纳米管制备Ag改性二氧化钛纳米颗粒的方法,采用水热‑液相沉积处理法制备,600℃下高温热处理,通过Ag改性与液相沉积处理工艺相结合,有效抑制了光生电子‑空穴对的复合,从而大幅度地提高了光催化降解甲基橙的活性,作为光催化剂,可用于水和空气中有机污染物的治理等方面,在光电及气敏方面亦具有潜在的应用价值。
Description
技术领域
本发明涉及光催化材料和太阳能利用领域,特别涉及一种基于二氧化钛纳米管制备Ag改性二氧化钛纳米颗粒的方法。
背景技术
纳米TiO2是一种重要的无机功能材料,具有湿敏、气敏、介电效应、光电转换、光致变色及优越的光催化性能,在传感器、介电材料、光电材料、自清洁材料、催化剂及载体等领域具有广泛的应用前景。TiO2纳米管具有纳米级TiO2粉体的性质,同时具有极大的比表面积和孔隙率,极大地改善了粉体TiO2的特性和应用范围。在催化性能方面,由于TiO2纳米管具有极大的比表面积和孔隙率,因此吸附能力相应提高,且具有良好的光渗透性,从而极大的提高了光催化效率。同时若能在管中装入更小的无机、有机、金属或者磁性纳米粒子,组装成复合纳米材料,也将会大大改善TiO2的光电、电磁及催化性能。同时,大量研究表明,对TiO2纳米材料进行贵金属粒子修饰如Pt、Au、Pd、Ag等,能有效抑制光生电子和空穴的复合,促进光生电子/空穴对的分离,显著提高TiO2的光催化性能及光电催化性能,甚至可以拓展TiO2纳米材料的吸收波长范围。
目前二氧化钛纳米管的合成与表征已成为纳米材料研究的一个热点领域,越来越受到科学家们的重视。学者们用模板法成功制得了二氧化钛纳米管;但是,该法制得的二氧化钛纳米管的管径大、管壁厚、比表面积小,在焙烧过程中容易坍塌破碎,制备过程及工艺复杂。有学者采用水热合成法制成二氧化钛纳米管,其管壁薄、管径小、比表面积大,性能更优,并且这种合成方法比较简单;但是,这种化学处理法得到的纳米管管壁比较薄,随着焙烧温度的不断升高,纳米管逐渐失去结构水,管壁层间距缩小,在进行高温热处理时管状结构容易被破坏,从而无法进行高温处理得到晶型结构较好且保持良好管状形貌结构的TiO2纳米管,故其光催化活性较低。考虑其管壁坍塌的原因可能有两个:(1)失水的过程中,由于二氧化钛粉碎而坍塌;(2)晶型转换而使得分子键错位而坍塌。
发明内容
本发明的目的在于克服现有技术中存在的缺点,提供一种基于二氧化钛纳米管制备Ag改性二氧化钛纳米颗粒的方法,通过该方法制得的Ag改性TiO2纳米颗粒光生电子-空穴分离效率高、光催化降解甲基橙活性高。
本发明的目的通过下述技术方案实现:
一种基于二氧化钛纳米管制备Ag改性二氧化钛纳米颗粒的方法,包括下述步骤:将TiO2纳米粉与NaOH溶液置于不锈钢水热反应釜中,110~140℃下水热反应12~48h,反应完毕后冷却至室温,取出白色沉淀物,用去离子水洗涤数次直至上清液为中性,然后用HCl溶液浸泡3~5h,继续用去离子水洗涤数次,直至上清液为中性,将白色沉淀物烘干,将烘干后的白色产物加入到0.05~0.15mol/L AgNO3溶液中,超声分散20~60min,搅拌1~3h,过滤得到沉淀物,用过量的0.05~0.15mol/L硫酸肼洗涤沉淀物以保证Ag+完全被还原,用去离子水洗净并过滤后置于氟钛酸铵和硼酸的混合液中,液相沉积40~80min后烘干,并于500~600℃焙烧1~3h,得到Ag改性TiO2纳米颗粒。
烘干后的白色产物与AgNO3溶液的配比为(0.1~0.3):50g/mL。
液相沉积所用混合液中氟钛酸铵和硼酸的摩尔比为1:3。
烘干后的白色产物与氟钛酸铵的配比为(0.1~0.3):0.0125g/mol。
烘干后的白色产物与氟钛酸铵和硼酸的混合液的配比为(0.1~0.3):250g/mL。
液相沉积的时间优选40min、60min或80min。
焙烧的温度优选500℃、550℃或600℃;焙烧的时间优选1h、2h或3h。
本发明与现有技术相比具有如下优点和效果:本发明采用水热-液相沉积处理法制备,600℃下高温热处理,通过Ag改性与液相沉积处理工艺相结合,有效抑制了光生电子-空穴对的复合,提高了光催化降解甲基橙的活性,作为光催化剂,可用于水和空气中有机污染物的治理等方面,在光电及气敏方面亦具有潜在的应用价值。
附图说明
图1是空心TiO2纳米颗粒(a)和Ag改性TiO2纳米颗粒(b)的TEM图。
图2是Ag改性TiO2纳米颗粒的EDS图。
图3是空心TiO2纳米颗粒和Ag改性TiO2纳米颗粒的UV-Vis漫反射谱图。
图4是空心TiO2纳米颗粒和Ag改性TiO2纳米颗粒的光催化降解甲基橙性能图。
具体实施方式
下面结合实施例对本发明做进一步详细的描述,但本发明的实施方式不限于此。
实施例1
将2g TiO2纳米粉与40mL10M NaOH溶液置于不锈钢水热反应釜中,110℃下水热反应12h,反应完毕后冷却至室温,取出白色沉淀物,用去离子水洗涤数次直至上清液为中性,然后用0.1M HCl溶液浸泡5h,继续用去离子水洗涤数次,直至上清液为中性,将白色沉淀物80℃烘干,称取0.2g烘干后的白色产物加入到50mL 0.05mol/L AgNO3溶液中,超声分散30min,搅拌1h,过滤所得到的沉淀物,用过量的0.1mol/L硫酸肼洗涤沉淀物以保证Ag+完全被还原,用去离子水洗净并过滤后置于125mL 0.1mol/L氟钛酸铵溶液和125mL 0.3mol/L硼酸溶液的混合液中,液相沉积40min,80℃烘干后继续600℃焙烧1h,得到Ag改性TiO2纳米颗粒。
实施例2:
将2g TiO2纳米粉与40mL10M NaOH溶液置于不锈钢水热反应釜中,140℃下水热反应48h,反应完毕后冷却至室温,取出白色沉淀物,用去离子水洗涤数次直至上清液为中性,然后用0.1M HCl溶液浸泡4h,继续用去离子水洗涤数次,直至上清液为中性,将白色沉淀物100℃烘干,称取0.2g烘干后的白色产物加入到50mL 0.15mol/L AgNO3溶液中,超声60min,搅拌2h,过滤所得到的沉淀物,用过量的0.15mol/L硫酸肼洗涤沉淀物以保证Ag+完全被还原,用去离子水洗净并过滤后置于125mL 0.1mol/L氟钛酸铵溶液和125mL 0.3mol/L硼酸溶液的混合液中,液相沉积80min,80℃烘干后继续600℃焙烧3h,得到Ag改性TiO2纳米颗粒。
对比例1
将2g TiO2纳米粉与40mL10M NaOH溶液置于不锈钢水热反应釜中,110℃下水热反应12h,反应完毕后冷却至室温,取出白色沉淀物,用去离子水洗涤数次直至上清液为中性,然后用0.1M HCl溶液浸泡5h,继续用去离子水洗涤数次,直至上清液为中性,将白色沉淀物80℃烘干,称取0.2g烘干后的白色产物置于125mL 0.1mol/L氟钛酸铵溶液和125mL0.3mol/L硼酸溶液的混合液中,液相沉积40min,80℃烘干后继续600℃焙烧1h,得到空心TiO2纳米颗粒。
对比例2:
将2g TiO2纳米粉与40mL10M NaOH溶液置于不锈钢水热反应釜中,140℃下水热反应48h,反应完毕后冷却至室温,取出白色沉淀物,用去离子水洗涤数次直至上清液为中性,然后用0.1M HCl溶液浸泡4h,继续用去离子水洗涤数次,直至上清液为中性,将白色沉淀物100℃烘干,称取0.2g烘干后的白色产物置于125mL 0.1mol/L氟钛酸铵溶液和125mL0.3mol/L硼酸溶液的混合液中,液相沉积80min,80℃烘干后继续600℃焙烧3h,得到空心TiO2纳米颗粒。
光催化活性评价:
以125W直管型高压汞灯(紫外主波长为365nm)作光源,向光催化反应器中加入浓度为20mg/L的甲基橙溶液400mL及0.4g TiO2样品TNL600、AgTNL600。在无光照下充空气磁力搅拌30min使催化剂与反应液充分混合,达到吸附/脱附平衡,并取样作测试以研究其吸附性能。同时将高压汞灯置于自制的自来水冷凝装置中,开启紫外灯预热,以便在实验开始时光照基本稳定。实验时,开启紫外灯,同时开启充气装置,向光催化反应***提供氧气并起到搅拌作用。每隔5min取样一次,离心分离20min,用日立UV-3010紫外可见分光光度计在300-800nm波长范围内扫描测定甲基橙溶液的吸光度。所有试验和测试都是在室温下进行的。
η为甲基橙溶液的脱色率,Ct和C0分别为甲基橙溶液的初始浓度和降解后浓度。
图1为空心TiO2纳米颗粒(a)和Ag改性TiO2纳米颗粒(b)的TEM图,由图1可见,空心TiO2纳米颗粒TNL600的平均尺寸为18nm左右,TiO2纳米颗粒中间有一空心结构,而Ag改性TiO2纳米颗粒已经无法观察到空心结构的存在,且进行修饰的Ag以微团的形式负载于纳米颗粒表面,并且纳米颗粒的尺寸有所增大,平均尺寸为28nm左右。
图2为Ag改性TiO2纳米颗粒EDS谱图,其中测得Ag的重量百分比大于6%,谱图中的C可能来自于实验过程中用来过滤沉积液或纳米管的滤纸,Cu来自承载样品的铜网。
图3为空心TiO2纳米颗粒和Ag改性TiO2纳米颗粒的紫外—可见扩散反射谱,采用直线外推法计算样品的吸收带边,已知本发明采用的锐钛矿TiO2粉末原料的光吸收带边为383nm,粒径约30nm。根据图3可见,空心TiO2纳米颗粒和Ag改性TiO2纳米颗粒的光吸收带边与体相锐钛矿相比有明显蓝移,空心TiO2纳米颗粒的光吸收带边为377nm,Ag改性TiO2纳米颗粒的光吸收带边为365nm,相对于原粉分别蓝移了6nm和18nm。同时可以看出Ag的修饰使TiO2纳米颗粒的全反射明显削弱。
图4为空心TiO2纳米颗粒和Ag改性TiO2纳米颗粒的光催化活性比较,根据(C/C0)vs.t线性回归求得空心TiO2纳米颗粒与Ag改性TiO2纳米颗粒及P25的光催化降解甲基橙溶液的表观速率常数分别为:0.08593,0.14045,0.05812,Ag改性TiO2纳米颗粒的光催化活性是空心TiO2纳米颗粒的1.5倍多,因此,Ag的改性修饰使得光催化降解甲基橙的活性得到大幅度提高。
最后应说明的是:以上仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换,但是凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种基于二氧化钛纳米管制备Ag改性二氧化钛纳米颗粒的方法,其特征在于包括以下步骤:将TiO2纳米粉与NaOH溶液置于不锈钢水热反应釜中,110~140℃下水热反应12~48h,反应完毕后冷却至室温,取出白色沉淀物,用去离子水洗涤数次直至上清液为中性,然后用HCl溶液浸泡3~5h,继续用去离子水洗涤数次,直至上清液为中性,将白色沉淀物烘干,将烘干后的白色产物加入到0.05~0.15mol/L AgNO3溶液中,超声分散20~60min,搅拌1~3h,过滤得到沉淀物,用过量的0.05~0.15mol/L硫酸肼洗涤沉淀物以保证Ag+完全被还原,用去离子水洗净并过滤后置于氟钛酸铵和硼酸的混合液中,液相沉积40~80min后烘干,并于500~600℃焙烧1~3h,得到Ag改性TiO2纳米颗粒。
2.根据权利要求1所述的基于二氧化钛纳米管制备Ag改性二氧化钛纳米颗粒的方法,其特征在于:烘干后的白色产物与AgNO3溶液的配比为(0.1~0.3):50g/mL。
3.根据权利要求1所述的基于二氧化钛纳米管制备Ag改性二氧化钛纳米颗粒的方法,其特征在于:液相沉积所用混合液中氟钛酸铵和硼酸的摩尔比为1:3。
4.根据权利要求1所述的基于二氧化钛纳米管制备Ag改性二氧化钛纳米颗粒的方法,其特征在于:烘干后的白色产物与氟钛酸铵的配比为(0.1~0.3):0.0125g/mol。
5.根据权利要求1所述的基于二氧化钛纳米管制备Ag改性二氧化钛纳米颗粒的方法,其特征在于:烘干后的白色产物与氟钛酸铵和硼酸的混合液的配比为(0.1~0.3):250g/mL。
6.根据权利要求1所述的基于二氧化钛纳米管制备Ag改性二氧化钛纳米颗粒的方法,其特征在于:液相沉积的时间为40min、60min或80min。
7.根据权利要求1所述的基于二氧化钛纳米管制备Ag改性二氧化钛纳米颗粒的方法,其特征在于:焙烧的温度为500℃、550℃或600℃;焙烧的时间为1h、2h或3h。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711432084.6A CN108311142A (zh) | 2017-12-26 | 2017-12-26 | 一种基于二氧化钛纳米管制备Ag改性二氧化钛纳米颗粒的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201711432084.6A CN108311142A (zh) | 2017-12-26 | 2017-12-26 | 一种基于二氧化钛纳米管制备Ag改性二氧化钛纳米颗粒的方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108311142A true CN108311142A (zh) | 2018-07-24 |
Family
ID=62892699
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201711432084.6A Pending CN108311142A (zh) | 2017-12-26 | 2017-12-26 | 一种基于二氧化钛纳米管制备Ag改性二氧化钛纳米颗粒的方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108311142A (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111298788A (zh) * | 2019-12-02 | 2020-06-19 | 上海纳米技术及应用国家工程研究中心有限公司 | 银负载有色一维介孔二氧化钛的制备方法及其产品和应用 |
CN112426881A (zh) * | 2020-11-30 | 2021-03-02 | 桂林理工大学 | 一种仿生纳米除味剂、其制备方法及应用 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1613556A (zh) * | 2004-09-23 | 2005-05-11 | 武汉理工大学 | Ag与TiO2多相纳晶复合薄膜光催化剂的原位制备方法 |
CN1973736A (zh) * | 2006-12-11 | 2007-06-06 | 张国栋 | 活性炭负载掺银TiO2光催化家用饮水机的净水柱 |
CN101182033A (zh) * | 2007-11-20 | 2008-05-21 | 中国科学院广州能源研究所 | 二氧化钛纳米管的制备方法 |
CN105336501A (zh) * | 2015-11-24 | 2016-02-17 | 石河子大学 | 纳米银和二氧化钛协同修饰氧化锌纳米线阵列及制备方法 |
CN106270500A (zh) * | 2016-09-30 | 2017-01-04 | 昆明理工大学 | 一种碳纳米管表面均匀包覆金属银的方法及装置 |
-
2017
- 2017-12-26 CN CN201711432084.6A patent/CN108311142A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1613556A (zh) * | 2004-09-23 | 2005-05-11 | 武汉理工大学 | Ag与TiO2多相纳晶复合薄膜光催化剂的原位制备方法 |
CN1973736A (zh) * | 2006-12-11 | 2007-06-06 | 张国栋 | 活性炭负载掺银TiO2光催化家用饮水机的净水柱 |
CN101182033A (zh) * | 2007-11-20 | 2008-05-21 | 中国科学院广州能源研究所 | 二氧化钛纳米管的制备方法 |
CN105336501A (zh) * | 2015-11-24 | 2016-02-17 | 石河子大学 | 纳米银和二氧化钛协同修饰氧化锌纳米线阵列及制备方法 |
CN106270500A (zh) * | 2016-09-30 | 2017-01-04 | 昆明理工大学 | 一种碳纳米管表面均匀包覆金属银的方法及装置 |
Non-Patent Citations (1)
Title |
---|
朱永法 等: "《光催化 环境净化与绿色能源应用探索》", 31 January 2015, 化学工业出版社 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111298788A (zh) * | 2019-12-02 | 2020-06-19 | 上海纳米技术及应用国家工程研究中心有限公司 | 银负载有色一维介孔二氧化钛的制备方法及其产品和应用 |
CN111298788B (zh) * | 2019-12-02 | 2022-07-12 | 上海纳米技术及应用国家工程研究中心有限公司 | 银负载有色一维介孔二氧化钛的制备方法及其产品和应用 |
CN112426881A (zh) * | 2020-11-30 | 2021-03-02 | 桂林理工大学 | 一种仿生纳米除味剂、其制备方法及应用 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107159313B (zh) | 一种核壳结构TiO2纳米管@Ti-MOF催化剂的制备方法 | |
Dong et al. | AgBr@ Ag/TiO2 core–shell composite with excellent visible light photocatalytic activity and hydrothermal stability | |
CN107200350B (zh) | 以玉米须为模板制备TiO2纳米管阵列光催化材料的方法 | |
CN102145280B (zh) | 稻壳活性炭/二氧化硅/二氧化钛复合材料的制备方法 | |
Wang et al. | Photocatalytic activity of hydrogen production from water over TiO2 with different crystal structures | |
Dong et al. | Construction of a novel N-doped oxygen vacancy-rich TiO2 N-TiO2− X/g-C3N4 S-scheme heterostructure for visible light driven photocatalytic degradation of 2, 4-dinitrophenylhydrazine | |
CN106622271A (zh) | 一种镍掺杂纳米钨酸铋可见光催化剂及其制备和应用 | |
CN111450858B (zh) | 一种复合光催化剂Ag/AgCl@Co3O4的制备方法及由此制得的复合光催化剂 | |
CN107159192B (zh) | 一种贵金属/TiO2混晶纳米棒组装多级结构的制备方法 | |
CN105728056A (zh) | 一种丝瓜络负载纳米二氧化钛光催化剂的制备方法 | |
CN111874988A (zh) | 基于多元素共掺杂TiO2纳米光催化材料的有机废水处理方法 | |
CN106215967A (zh) | 一种g‑C3N4量子点、Ag量子点敏化Bi2MoO6纳米片的制备方法 | |
CN108311142A (zh) | 一种基于二氧化钛纳米管制备Ag改性二氧化钛纳米颗粒的方法 | |
Maimaiti et al. | Synthesis and visible-light photocatalytic CO2/H2O reduction to methyl formate of TiO2 nanoparticles coated by aminated cellulose | |
CN107626297B (zh) | 一种空心微球状铋/钒酸铋复合光催化剂及其制备方法和应用 | |
CN109647437A (zh) | 一种CuS掺杂纳米TiO2光催化剂、制备方法及其应用 | |
CN107570159A (zh) | 一种制备高性能黑色TiO2光催化剂的方法 | |
CN108640149B (zh) | 二氧化钛纳米空心球及其制备方法 | |
Yang et al. | Single-step preparation, characterization and photocatalytic mechanism of mesoporous Fe-doped sulfated titania | |
Moniruddin et al. | Nanoassembly of perovskite-based photocatalysts in a nanoconfined system for photocatalytic H2 production under visible light | |
CN106964352B (zh) | 新型光催化材料TiO2@Fe2O3、SrTiO3@Fe2O3的制备及应用 | |
CN108940325A (zh) | 一种二元复合半导体光催化剂材料Ag2CrO4/BiOI及其制备与应用 | |
CN108295897B (zh) | 一种复合可见光光催化剂Ag2CO3/TiO2/UIO-66-(COOH)2及有机物降解应用 | |
CN106423259B (zh) | 一种利用天然凹凸棒石制备Ag-AgBr/Al-MCM-41复合功能材料的方法 | |
CN104588047A (zh) | 一种光催化三氧化二铁/氯氧化铋复合材料的制备方法 |
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 | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180724 |