CN112371178A - 一种聚苯胺接枝ZnFe2O4中空微球的复合光催化材料及其制法 - Google Patents
一种聚苯胺接枝ZnFe2O4中空微球的复合光催化材料及其制法 Download PDFInfo
- Publication number
- CN112371178A CN112371178A CN202011322134.7A CN202011322134A CN112371178A CN 112371178 A CN112371178 A CN 112371178A CN 202011322134 A CN202011322134 A CN 202011322134A CN 112371178 A CN112371178 A CN 112371178A
- Authority
- CN
- China
- Prior art keywords
- znfe
- polyaniline
- hollow
- hollow microspheres
- grafted
- 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.)
- Withdrawn
Links
- 239000004005 microsphere Substances 0.000 title claims abstract description 91
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 33
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims description 8
- 229910001308 Zinc ferrite Inorganic materials 0.000 claims abstract description 60
- 230000004048 modification Effects 0.000 claims abstract description 4
- 238000012986 modification Methods 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 44
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 239000012153 distilled water Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000012298 atmosphere Substances 0.000 claims description 18
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- QLNOVKKVHFRGMA-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical group [CH2]CC[Si](OC)(OC)OC QLNOVKKVHFRGMA-UHFFFAOYSA-N 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 11
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 11
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 10
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000004246 zinc acetate Substances 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 229940010514 ammonium ferrous sulfate Drugs 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 11
- 230000009471 action Effects 0.000 abstract description 6
- 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 6
- 229940043267 rhodamine b Drugs 0.000 abstract description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 5
- 238000005215 recombination Methods 0.000 abstract description 5
- 230000006798 recombination Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 13
- 150000001448 anilines Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- -1 aromatic imine Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000879 imine group Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229960000314 zinc acetate Drugs 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
- B01J31/02—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
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J35/33—Electric or magnetic 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
- B01J35/30—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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
本发明涉及光催化降解领域,且公开了一种聚苯胺接枝ZnFe2O4中空微球的复合光催化材料,ZnFe2O4中空微球具有更高的比表面积,光化学催化位点十分丰富,聚苯胺在ZnFe2O4中空微球表面原位聚合,通过化学键共价连接,使两者很难发生脱落和分离,由于ZnFe2O4的价带和导带之间的电位与聚苯胺的最高占据轨道和最低空轨道之间的电位相匹配,通过聚苯胺对ZnFe2O4进行接枝改性,会提高ZnFe2O4光生电子和空穴的分离效率,有效抑制光生载流子的复合和重组,提高了ZnFe2O4的光催化降解活性,聚苯胺可以能通过π‑π作用吸附和静电作用,吸附罗丹明B,有利于复合光催化剂对罗丹明B的接触和降解过程,实现高效的光催化降解。
Description
技术领域
本发明涉及光催化降解领域,具体为一种聚苯胺接枝ZnFe2O4中空微球的复合光催化材料及其制法。
背景技术
近几十年来,大自然环境污染日益加重,可以通过光催化反应能分解出多种环保所关注的治理重金属污染、有机物,在医疗上还可用于消毒、脱色等,其中光催化技术在重金属污染物废水降解方面的应用深受到国内外学者的关注,其主要原因是稳定性好、研究效益好、可见光催化活性高的光催化剂是实现光催化技术走向在实际生活应用中的前提,在目前阶段,光催化技术存在着一些问题,光催化反应量子效率低,限制工业大规模的应用,光催化剂的禁带宽度较宽,对可见光的利用率很低,因此目前阶段制备具有量子效率高、对可见光高度响应的高效应活性光催化材料已成为各领域关注和我们所研究的重点。
其中常见的光催化剂金属氧化物、硫化物,如TiO2、ZnFe2O4、CdS、WO3等,利用水热法可以制备出多种特殊形貌的光催化剂,且所制备的光催化剂的催化性能优异,一些特殊形貌的光催化剂具有比表面积大、光生电子-空穴对复合率低及光能利用率高等优点,如纳米线、纳米棒、纳米片、纳米管、核壳结构,ZnFe2O4其特点是两者之间的导带与价带之间的能量差较小,光化学活性较高,并且合成简单方便,环保无毒,同时具有电磁响应特性,便于光催化剂的磁性回收,但是ZnFe2O4的光生电子和空穴容易重组和复合,严重影响了其光催化活性,因此需要进一步提高ZnFe2O4光催化剂的催化活性。
(一)解决的技术问题
针对现有技术的不足,本发明提供了一种聚苯胺接枝ZnFe2O4中空微球的复合光催化材料及其制法,解决了ZnFe2O4的光生电子和空穴容易重组和复合,严重影响了其光催化活性的问题。
(二)技术方案
为实现上述目的,本发明提供如下技术方案:一种聚苯胺接枝ZnFe2O4中空微球的复合光催化材料,所述聚苯胺接枝ZnFe2O4中空微球的复合光催化材料制备方法包括以下步骤:
(1)将硫酸亚铁铵、醋酸锌和十二烷基苯磺酸钠和蒸馏水溶剂加入水热反应釜中,在170-190℃反应18-30h,过滤溶剂、蒸馏水和乙醇洗涤并干燥,产物在管式气氛炉中,在500-550℃,煅烧2-3h,得到ZnFe2O4中空微球;
(2)将ZnFe2O4中空微球分散在无水甲苯溶液中,搅拌条件下滴加入N-[3-(三甲氧基甲硅基)丙基]苯胺,在氮气氛围下,将混合溶液加热到80-100℃回流反应10-15h,产物通过甲苯和甲醇交替洗涤,并干燥,制备得到芳亚胺化改性ZnFe2O4中空微球;
(3)向质量分数为4-8%的醋酸溶液中加入芳亚胺化改性ZnFe2O4中空微球,超声分散均匀后加入苯胺,缓慢滴加过硫酸铵溶液,匀速搅拌反应1-3h,使用蒸馏水和丙酮离心洗涤并干燥,制备得到聚苯胺接枝ZnFe2O4中空微球的复合光催化材料。
优选的,所述步骤(1)中的硫酸亚铁铵、醋酸锌和十二烷基苯磺酸钠的质量比为300-320:100:350-420。
优选的,所述步骤(1)中的管式气氛炉装置包括进气阀门,进气阀门固定连接有炉盖,炉盖下方固定连接有冷热循环器,冷热循环器下方活动连接炉管,炉管下方固定连接加热片,加热片下方设置显示器,显示器左方固定连接旋转器,旋转器右上方固定连接出气阀门。
优选的,所述步骤(2)中的ZnFe2O4中空微球和N-[3-(三甲氧基甲硅基)丙基]苯胺的质量比为100:350-450。
优选的,所述步骤(3)中的芳亚胺化改性ZnFe2O4中空微球、苯胺和过硫酸铵的质量比为100:8-15:20-40。
(三)有益的技术效果
与现有技术相比,本发明具备以下实验原理和有益技术效果:
该一种聚苯胺接枝ZnFe2O4中空微球的复合光催化材料,在十二烷基苯磺酸钠表面活性剂的作用下,ZnFe2O4纳米粒子定向聚集,形成具有分级结构的微纳米级的三维空心球结构,从而使ZnFe2O4中空微球具有更高的比表面积,光化学催化位点十分丰富,有利于提高与光辐射的接触,促进电子跃迁,产生更多的光生电子和空穴。
该一种聚苯胺接枝ZnFe2O4中空微球的复合光催化材料,由水热法制备的ZnFe2O4表面中含有丰富的羟基基团,与N-[3-(三甲氧基甲硅基)丙基]苯胺反应,得到芳亚胺化改性ZnFe2O4中空微球,进一步在过硫酸铵引发作用下,使改性ZnFe2O4中空微球的芳亚胺基团与苯胺发生聚合反应,从而使聚苯胺在ZnFe2O4中空微球表面原位聚合,通过化学键共价连接,使ZnFe2O4中空微球和聚苯胺紧密结合,相对比于物理混合来说,化学键共价连接使两者很难发生脱落和分离,由于ZnFe2O4的价带和导带之间的电位与聚苯胺的最高占据轨道和最低空轨道之间的电位相匹配,通过聚苯胺对ZnFe2O4进行接枝改性,会提高ZnFe2O4光生电子和空穴的分离效率,有效抑制光生载流子的复合和重组,从而提高了ZnFe2O4的光催化降解活性。
该一种聚苯胺接枝ZnFe2O4中空微球的复合光催化材料,聚苯胺可以能通过π-π作用吸附和静电作用,吸附含有共轭结构的离子型染料罗丹明B,有利于复合光催化剂对罗丹明B的接触和降解过程,实现高效的光催化降解,同时ZnFe2O4中空微球具有良好的磁性,使复合光催化材料具有一定的磁性吸附和磁性回收效果。
附图说明
图1是管式气氛炉装置正面示意图;
图2是炉管内局部放大示意图;
图3是旋转器内齿轮局部放大示意图。
1-管式气氛炉体;2-进气阀门;3-炉盖;4-冷热循环器;5-炉管;6-加热片;7-显示器;8-旋转器;9出气阀门。
具体实施方式
为实现上述目的,本发明提供如下具体实施方式和实施例:一种聚苯胺接枝ZnFe2O4中空微球的复合光催化材料,制备方法包括以下步骤:
(1)将质量比为300-320:100:350-420的硫酸亚铁铵、醋酸锌和十二烷基苯磺酸钠,加入到蒸馏水溶剂中,置于水热反应釜中,在170-190℃反应18-30h,过滤溶剂、蒸馏水和乙醇洗涤并干燥,产物放入管式气氛炉中,管式气氛炉装置包括进气阀门,进气阀门固定连接有炉盖,炉盖下方固定连接有冷热循环器,冷热循环器下方活动连接炉管,炉管下方固定连接加热片,加热片下方设置显示器,显示器左方固定连接旋转器,旋转器右上方固定连接出气阀门,在500-550℃,煅烧2-3h,得到ZnFe2O4中空微球;
(2)将ZnFe2O4中空微球分散在无水甲苯溶液中,搅拌条件下滴加入N-[3-(三甲氧基甲硅基)丙基]苯胺,其中ZnFe2O4中空微球和N-[3-(三甲氧基甲硅基)丙基]苯胺的质量比为100:350-450,在氮气氛围下,将混合溶液加热到80-100℃回流反应10-15h,产物通过甲苯和甲醇交替洗涤,并干燥,制备得到芳亚胺化改性ZnFe2O4中空微球;
(3)向质量分数为4-8%的醋酸溶液中加入芳亚胺化改性ZnFe2O4中空微球,超声分散均匀后加入苯胺,缓慢滴加过硫酸铵溶液,其中芳亚胺化改性ZnFe2O4中空微球、苯胺和过硫酸铵的质量比为100:8-15:20-40,匀速搅拌反应1-3h,使用蒸馏水和丙酮离心洗涤并干燥,制备得到聚苯胺接枝ZnFe2O4中空微球的复合光催化材料。
实施例1
(1)将质量比为300:100:350的硫酸亚铁铵、醋酸锌和十二烷基苯磺酸钠,加入到蒸馏水溶剂中,置于水热反应釜中,在170℃反应18h,过滤溶剂、蒸馏水和乙醇洗涤并干燥,产物放入管式气氛炉中,管式气氛炉装置包括进气阀门,进气阀门固定连接有炉盖,炉盖下方固定连接有冷热循环器,冷热循环器下方活动连接炉管,炉管下方固定连接加热片,加热片下方设置显示器,显示器左方固定连接旋转器,旋转器右上方固定连接出气阀门,在500℃,煅烧2h,得到ZnFe2O4中空微球;
(2)将ZnFe2O4中空微球分散在无水甲苯溶液中,搅拌条件下滴加入N-[3-(三甲氧基甲硅基)丙基]苯胺,其中ZnFe2O4中空微球和N-[3-(三甲氧基甲硅基)丙基]苯胺的质量比为100:350,在氮气氛围下,将混合溶液加热到80℃回流反应10h,产物通过甲苯和甲醇交替洗涤,并干燥,制备得到芳亚胺化改性ZnFe2O4中空微球;
(3)向质量分数为4%的醋酸溶液中加入芳亚胺化改性ZnFe2O4中空微球,超声分散均匀后加入苯胺,缓慢滴加过硫酸铵溶液,其中芳亚胺化改性ZnFe2O4中空微球、苯胺和过硫酸铵的质量比为100:8:20,匀速搅拌反应1h,使用蒸馏水和丙酮离心洗涤并干燥,制备得到聚苯胺接枝ZnFe2O4中空微球的复合光催化材料。
实施例2
(1)将质量比为310:100:385的硫酸亚铁铵、醋酸锌和十二烷基苯磺酸钠,加入到蒸馏水溶剂中,置于水热反应釜中,在180℃反应24h,过滤溶剂、蒸馏水和乙醇洗涤并干燥,产物放入管式气氛炉中,管式气氛炉装置包括进气阀门,进气阀门固定连接有炉盖,炉盖下方固定连接有冷热循环器,冷热循环器下方活动连接炉管,炉管下方固定连接加热片,加热片下方设置显示器,显示器左方固定连接旋转器,旋转器右上方固定连接出气阀门,在525℃,煅烧2.5h,得到ZnFe2O4中空微球;
(2)将ZnFe2O4中空微球分散在无水甲苯溶液中,搅拌条件下滴加入N-[3-(三甲氧基甲硅基)丙基]苯胺,其中ZnFe2O4中空微球和N-[3-(三甲氧基甲硅基)丙基]苯胺的质量比为100:400,在氮气氛围下,将混合溶液加热到90℃回流反应13h,产物通过甲苯和甲醇交替洗涤,并干燥,制备得到芳亚胺化改性ZnFe2O4中空微球;
(3)向质量分数为6%的醋酸溶液中加入芳亚胺化改性ZnFe2O4中空微球,超声分散均匀后加入苯胺,缓慢滴加过硫酸铵溶液,其中芳亚胺化改性ZnFe2O4中空微球、苯胺和过硫酸铵的质量比为100:11.5:30,匀速搅拌反应2h,使用蒸馏水和丙酮离心洗涤并干燥,制备得到聚苯胺接枝ZnFe2O4中空微球的复合光催化材料。
实施例3
(1)将质量比为300:100:420的硫酸亚铁铵、醋酸锌和十二烷基苯磺酸钠,加入到蒸馏水溶剂中,置于水热反应釜中,在175℃反应25h,过滤溶剂、蒸馏水和乙醇洗涤并干燥,产物放入管式气氛炉中,管式气氛炉装置包括进气阀门,进气阀门固定连接有炉盖,炉盖下方固定连接有冷热循环器,冷热循环器下方活动连接炉管,炉管下方固定连接加热片,加热片下方设置显示器,显示器左方固定连接旋转器,旋转器右上方固定连接出气阀门,在530℃,煅烧3h,得到ZnFe2O4中空微球;
(2)将ZnFe2O4中空微球分散在无水甲苯溶液中,搅拌条件下滴加入N-[3-(三甲氧基甲硅基)丙基]苯胺,其中ZnFe2O4中空微球和N-[3-(三甲氧基甲硅基)丙基]苯胺的质量比为100:420,在氮气氛围下,将混合溶液加热到85℃回流反应13h,产物通过甲苯和甲醇交替洗涤,并干燥,制备得到芳亚胺化改性ZnFe2O4中空微球;
(3)向质量分数为8%的醋酸溶液中加入芳亚胺化改性ZnFe2O4中空微球,超声分散均匀后加入苯胺,缓慢滴加过硫酸铵溶液,其中芳亚胺化改性ZnFe2O4中空微球、苯胺和过硫酸铵的质量比为100:15:25,匀速搅拌反应2h,使用蒸馏水和丙酮离心洗涤并干燥,制备得到聚苯胺接枝ZnFe2O4中空微球的复合光催化材料。
实施例4
(1)将质量比为320:100:420的硫酸亚铁铵、醋酸锌和十二烷基苯磺酸钠,加入到蒸馏水溶剂中,置于水热反应釜中,在190℃反应30h,过滤溶剂、蒸馏水和乙醇洗涤并干燥,产物放入管式气氛炉中,管式气氛炉装置包括进气阀门,进气阀门固定连接有炉盖,炉盖下方固定连接有冷热循环器,冷热循环器下方活动连接炉管,炉管下方固定连接加热片,加热片下方设置显示器,显示器左方固定连接旋转器,旋转器右上方固定连接出气阀门,在550℃,煅烧3h,得到ZnFe2O4中空微球;
(2)将ZnFe2O4中空微球分散在无水甲苯溶液中,搅拌条件下滴加入N-[3-(三甲氧基甲硅基)丙基]苯胺,其中ZnFe2O4中空微球和N-[3-(三甲氧基甲硅基)丙基]苯胺的质量比为100:450,在氮气氛围下,将混合溶液加热到100℃回流反应15h,产物通过甲苯和甲醇交替洗涤,并干燥,制备得到芳亚胺化改性ZnFe2O4中空微球;
(3)向质量分数为8%的醋酸溶液中加入芳亚胺化改性ZnFe2O4中空微球,超声分散均匀后加入苯胺,缓慢滴加过硫酸铵溶液,其中芳亚胺化改性ZnFe2O4中空微球、苯胺和过硫酸铵的质量比为100:15:40,匀速搅拌反应3h,使用蒸馏水和丙酮离心洗涤并干燥,制备得到聚苯胺接枝ZnFe2O4中空微球的复合光催化材料。
对比例1
(1)将质量比为280:100:315的硫酸亚铁铵、醋酸锌和十二烷基苯磺酸钠,加入到蒸馏水溶剂中,置于水热反应釜中,在180℃反应20h,过滤溶剂、蒸馏水和乙醇洗涤并干燥,产物放入管式气氛炉中,管式气氛炉装置包括进气阀门,进气阀门固定连接有炉盖,炉盖下方固定连接有冷热循环器,冷热循环器下方活动连接炉管,炉管下方固定连接加热片,加热片下方设置显示器,显示器左方固定连接旋转器,旋转器右上方固定连接出气阀门,在500℃,煅烧2h,得到ZnFe2O4中空微球;
(2)将ZnFe2O4中空微球分散在无水甲苯溶液中,搅拌条件下滴加入N-[3-(三甲氧基甲硅基)丙基]苯胺,其中ZnFe2O4中空微球和N-[3-(三甲氧基甲硅基)丙基]苯胺的质量比为100:320,在氮气氛围下,将混合溶液加热到90℃回流反应12h,产物通过甲苯和甲醇交替洗涤,并干燥,制备得到芳亚胺化改性ZnFe2O4中空微球;
(3)向质量分数为2%的醋酸溶液中加入芳亚胺化改性ZnFe2O4中空微球,超声分散均匀后加入苯胺,缓慢滴加过硫酸铵溶液,其中芳亚胺化改性ZnFe2O4中空微球、苯胺和过硫酸铵的质量比为100:5:13,匀速搅拌反应2h,使用蒸馏水和丙酮离心洗涤并干燥,制备得到聚苯胺接枝ZnFe2O4中空微球的复合光催化材料。
向浓度为0.5%的罗丹明B溶液中,加入2%的聚苯胺接枝ZnFe2O4中空微球的复合光催化材料,以20W日光灯管作为光源,辐射光照3h,使用UV1900双光束紫外可见分光光度计测定降解后的罗丹明B的浓度,并计算降解率,测试标准为GB/T 23762-2020。
Claims (5)
1.一种聚苯胺接枝ZnFe2O4中空微球的复合光催化材料,其特征在于:所述聚苯胺接枝ZnFe2O4中空微球的复合光催化材料制备方法包括以下步骤:
(1)将硫酸亚铁铵、醋酸锌和十二烷基苯磺酸钠和蒸馏水溶剂加入水热反应釜中,在170-190℃反应18-30h,过滤溶剂、蒸馏水和乙醇洗涤并干燥,产物在管式气氛炉中,在500-550℃,煅烧2-3h,得到ZnFe2O4中空微球;
(2)将ZnFe2O4中空微球分散在无水甲苯溶液中,搅拌条件下滴加入N-[3-(三甲氧基甲硅基)丙基]苯胺,在氮气氛围下,将混合溶液加热到80-100℃回流反应10-15h,产物通过甲苯和甲醇交替洗涤,并干燥,制备得到芳亚胺化改性ZnFe2O4中空微球;
(3)向质量分数为4-8%的醋酸溶液中加入芳亚胺化改性ZnFe2O4中空微球,超声分散均匀后加入苯胺,缓慢滴加过硫酸铵溶液,匀速搅拌反应1-3h,使用蒸馏水和丙酮离心洗涤并干燥,制备得到聚苯胺接枝ZnFe2O4中空微球的复合光催化材料。
2.根据权利要求1所述的一种聚苯胺接枝ZnFe2O4中空微球的复合光催化材料,其特征在于:所述步骤(1)中的硫酸亚铁铵、醋酸锌和十二烷基苯磺酸钠的质量比为300-320:100:350-420。
3.根据权利要求1所述的一种聚苯胺接枝ZnFe2O4中空微球的复合光催化材料,其特征在于:所述步骤(1)中的管式气氛炉装置包括进气阀门,进气阀门固定连接有炉盖,炉盖下方固定连接有冷热循环器,冷热循环器下方活动连接炉管,炉管下方固定连接加热片,加热片下方设置显示器,显示器左方固定连接旋转器,旋转器右上方固定连接出气阀门。
4.根据权利要求1所述的一种聚苯胺接枝ZnFe2O4中空微球的复合光催化材料,其特征在于:所述步骤(2)中的ZnFe2O4中空微球和N-[3-(三甲氧基甲硅基)丙基]苯胺的质量比为100:350-450。
5.根据权利要求1所述的一种聚苯胺接枝ZnFe2O4中空微球的复合光催化材料,其特征在于:所述步骤(2)中的芳亚胺化改性ZnFe2O4中空微球、苯胺和过硫酸铵的质量比为100:8-15:20-40。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011322134.7A CN112371178A (zh) | 2020-11-23 | 2020-11-23 | 一种聚苯胺接枝ZnFe2O4中空微球的复合光催化材料及其制法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011322134.7A CN112371178A (zh) | 2020-11-23 | 2020-11-23 | 一种聚苯胺接枝ZnFe2O4中空微球的复合光催化材料及其制法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN112371178A true CN112371178A (zh) | 2021-02-19 |
Family
ID=74587453
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011322134.7A Withdrawn CN112371178A (zh) | 2020-11-23 | 2020-11-23 | 一种聚苯胺接枝ZnFe2O4中空微球的复合光催化材料及其制法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112371178A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113019447A (zh) * | 2021-03-05 | 2021-06-25 | 华东理工大学 | 一种核壳结构的聚苯胺包覆酚醛树脂催化剂及其制备方法 |
-
2020
- 2020-11-23 CN CN202011322134.7A patent/CN112371178A/zh not_active Withdrawn
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113019447A (zh) * | 2021-03-05 | 2021-06-25 | 华东理工大学 | 一种核壳结构的聚苯胺包覆酚醛树脂催化剂及其制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Zhu et al. | Synthesis of novel ternary photocatalyst Ag3PO4/Bi2WO6/multi-walled carbon nanotubes and its enhanced visible-light photoactivity for photodegradation of norfloxacin | |
CN107159264A (zh) | 一种高效全光谱响应CuS/石墨烯复合光催化剂及其制备方法 | |
CN110227453B (zh) | 一种AgCl/ZnO/GO复合可见光催化剂的制备方法 | |
CN103861621B (zh) | 一种Bi7O9I3/石墨烯复合可见光催化剂及其制备方法 | |
CN113145134B (zh) | 一种基于矿物复合材料的可见光催化剂及其制备方法 | |
CN110813376A (zh) | 一种聚吡咯修饰的纳米溴氧化铋光催化材料及其制备方法和应用 | |
CN106311206A (zh) | 二氧化钛/石墨烯复合纳米光催化剂及其制备方法与应用 | |
CN104383947A (zh) | 一种磷酸银/二氧化钛纳米复合材料及其制备方法 | |
Chen et al. | Terephthalate acid decorated TiO2 for visible light driven photocatalysis mediated via ligand-to-metal charge transfer (LMCT) | |
CN104258857A (zh) | 一种铬酸银-氧化石墨烯复合光催化材料及其制备方法 | |
Ma et al. | A recyclable 3D gC 3 N 4 based nanocellulose aerogel composite for photodegradation of organic pollutants | |
CN111632614A (zh) | 三维花瓣状NiAl-LDH/Ti3C2复合光催化剂及其制备方法和应用 | |
CN104399535A (zh) | 一种磁性配合物基催化剂的制备方法和应用 | |
CN111992255B (zh) | 用于去除水中双酚A的片状g-C3N4/ZIF-8/AgBr复合材料及其制备方法 | |
CN112191259A (zh) | 一种MXene/Au光催化固氮材料、其制备方法及应用 | |
CN112246283A (zh) | 一种钨酸铋@MIL-100(Fe)复合材料及其制备方法和应用 | |
CN112371178A (zh) | 一种聚苯胺接枝ZnFe2O4中空微球的复合光催化材料及其制法 | |
CN101708454B (zh) | 负载ZnO纳米颗粒的薄片状镁铝复合氧化物及其制备和应用 | |
CN109650439B (zh) | 大尺寸自组装二氧化钛微球及其制备方法和应用 | |
CN109603825A (zh) | 一种埃洛石纳米管负载等离子体共振光催化剂及其制备方法 | |
CN113101980A (zh) | 一种具有可见光催化活性的TiO2/UiO-66复合材料的制备方法和应用 | |
CN117225443A (zh) | g-C3N4/TiO2(B)S型异质结光催化剂的制备方法及应用 | |
CN115849441B (zh) | 一种富氧空位Bi12O17Cl2超薄纳米片及其制备方法和应用 | |
CN114100657B (zh) | 一种α-Fe2O3/LaFeO3/g-C3N4/MXene材料及其制备方法和应用 | |
CN115069302B (zh) | 一种高效可见光催化材料及其制备方法和应用 |
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 | ||
WW01 | Invention patent application withdrawn after publication |
Application publication date: 20210219 |
|
WW01 | Invention patent application withdrawn after publication |