CN113457704A - 一种Fe2O3-ZnO/g-C3N4复合材料及其制备方法和应用 - Google Patents
一种Fe2O3-ZnO/g-C3N4复合材料及其制备方法和应用 Download PDFInfo
- Publication number
- CN113457704A CN113457704A CN202110635338.4A CN202110635338A CN113457704A CN 113457704 A CN113457704 A CN 113457704A CN 202110635338 A CN202110635338 A CN 202110635338A CN 113457704 A CN113457704 A CN 113457704A
- Authority
- CN
- China
- Prior art keywords
- solution
- zno
- precipitate
- composite material
- methanol
- 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.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000000463 material Substances 0.000 title description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002131 composite material Substances 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002244 precipitate Substances 0.000 claims abstract description 22
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 231100000719 pollutant Toxicity 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 4
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 12
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004098 Tetracycline Substances 0.000 claims description 12
- 229960003405 ciprofloxacin Drugs 0.000 claims description 12
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 12
- 229960002180 tetracycline Drugs 0.000 claims description 12
- 229930101283 tetracycline Natural products 0.000 claims description 12
- 235000019364 tetracycline Nutrition 0.000 claims description 12
- 239000000356 contaminant Substances 0.000 claims description 8
- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 6
- 150000003522 tetracyclines Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000013032 photocatalytic reaction Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 claims 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 29
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 53
- 239000011787 zinc oxide Substances 0.000 description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 35
- 230000015556 catabolic process Effects 0.000 description 18
- 238000006731 degradation reaction Methods 0.000 description 18
- 230000001699 photocatalysis Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 231100000049 endocrine disruptor Toxicity 0.000 description 2
- 239000000598 endocrine disruptor Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 206010006187 Breast cancer Diseases 0.000 description 1
- 208000026310 Breast neoplasm Diseases 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229940090668 parachlorophenol Drugs 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (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
本发明提供一种Fe2O3‑ZnO/g‑C3N4复合材料的制备方法,包括:1)将g‑C3N4分散于甲醇溶液中,得溶液A;2)将Zn(NO3)2·6H2O和Fe(NO3)3·9H2O共溶于甲醇溶液中,得溶液B;3)将二甲基咪唑溶于甲醇溶液中得溶液C;4)先将溶液A和溶液B混匀得混合液,然后将溶液C缓慢滴加于混合液中,于室温下搅拌使均匀混合后沉淀,得沉淀物;5)将所述沉淀物以甲醇洗涤并干燥;6)将干燥后的沉淀物均匀研磨后转移到管式加热炉,空气氛围中加热到550℃,煅烧即得。本发明还提供了该复合材料及其在光催化降解水中污染物中的应用。本发明提供的复合材料在可见光条件下能够高效快速去除水中双酚A。
Description
技术领域
本发明属于光催化材料及水净化处理技术领域,具体地涉及用于去除水中污染物的Fe2O3-ZnO/g-C3N4复合材料及其制备方法和应用。
背景技术
双酚A(BPA)是一种典型的内分泌干扰物(EDCs),自合成以来应用广泛。其不仅可以用于生产塑料、环氧树脂、聚砜树脂等高分子材料,也可用于农药、涂料的生产。统计结果表明,2016年全球共生产约为800万吨的BPA,预计2022年该数值将增加到1060万吨。这种有害化学物质通过人类的生产生活排放到水体、空气当中,或与人类皮肤直接接触,不仅对环境造成严重的污染,同时严重影响了人类的身体健康。高暴露水平的BPA可能会导致糖尿病、心血管疾病、乳腺癌等疾病的发生。因此,如何高效清洁去除BPA是目前亟待解决的问题。
常用的BPA降解和去除技术包括生物法、物理吸附法和化学氧化法。其中化学氧化法中的光催化技术,因其符合绿色化学原理、工艺简单且无二次污染而受到广泛的关注。
传统的光催化材料存在两大重要缺陷:一是光催化材料光谱响应范围窄,反应过程中只能吸收太阳光中含量极少的的紫外光部分,对太阳光利用率低;二是光催化反应量子效率低。因此,提高光催化材料催化性能的关键是拓宽其光谱响应范围和降低电子空穴对的复合率。在探索可见光催化剂的过程中,研究者们从结构的角度出发,开展了一系列的传统宽禁带宽度半导体光催化材料的改性工作,包括金属负载、离子掺杂和半导体复合等,使原本仅能在紫外光响应的半导体材料的吸收光谱拓宽至可见光范围。
类石墨相氮化碳(g-C3N4)是一种非金属聚合物半导体材料,具有典型的片层结构。在室温下结构稳定,对可见光能够产生响应(半导体带隙2.7eV),且光催化活性高、稳定性好、无毒无害、原料价格便宜,适用于光催化领域。然而其比表面积较小,电子空穴对复合率高,在污染水体中难以分离,易发生团聚,因而限制了其广泛应用。研究表明,构建基于g-C3N4的异质结是增强原始g-C3N4光催化性能最通用的策略,可以起双重作用:提高电子-空穴对的分离效率,并使载流子具有更强的氧化还原能力。氧化锌(ZnO)与g-C3N4能带匹配优越,被认为是偶联的合适候选物,其可以合成高效的异质结。例如,一种高级氧化催化剂C3N4-Cg/ZnO的制备方法和应用(CN202011556000.1)。然而,由于不同的晶体结构和晶格参数不利于实现晶格匹配,因此难以在g-C3N4和ZnO之间建立紧密的界面接触。李发堂在其专利(CN201710284146.7)中选用氧化铝(Al2O3)作为g-C3N4和ZnO之间的媒介,构筑三元异质结对甲基蓝进行光催化降解。唐辉在其专利(CN202010213411.4)中将氧化锌(ZnO)和二氧化钛(TiO2)负载到g-C3N4上。
发明内容
本发明的目的是针对上述现有技术存在的问题和需求,本发明利用两种常见的金属氧化物半导体材料氧化锌(ZnO)和氧化铁(Fe2O3)与g-C3N4进行偶联,选用Fe2O3作为ZnO和g-C3N4的媒介,增进ZnO和g-C3N4之间的界面接触,制备得到了Fe2O3-ZnO/g-C3N4三元复合光催化剂,构成Z形异质结,从而提高复合材料的光催化活性。可在可见光条件下高效快速的去除水中的双酚A,拥有广泛的应用前景。
本发明提供的技术方案具体如下:
一种Fe2O3-ZnO/g-C3N4复合材料的制备方法,包括:
1)将g-C3N4分散于甲醇中,得到溶液A;
2)将Zn(NO3)2·6H2O和Fe(NO3)3·9H2O共溶于甲醇中,得溶液B;
3)将二甲基咪唑溶于甲醇中得到溶液C;
4)先将溶液A和溶液B混合均匀得到混合液,然后将溶液C缓慢滴加于混合液中,于室温下搅拌使均匀混合后沉淀,得到沉淀物;
5)将所述沉淀物以甲醇洗涤并干燥;
6)将干燥后的沉淀物均匀研磨后转移到管式加热炉,空气氛围中加热到550℃,煅烧即制备得至Fe2O3-ZnO/g-C3N4复合材料。
在根据本发明的一个实施方案中,所述g-C3N4是通过包括下述步骤的方法制备得到的:将尿素于空气氛围中以550℃煅烧;然后将煅烧产物用超声洗涤30min后再以去离子水洗涤数次后烘干,即得g-C3N4;
优选地,以速率5℃/min梯度升温至550℃,煅烧4h。
在根据本发明的一个实施方案中,Fe(NO3)3·9H2O、Zn(NO3)2·6H2O、二甲基咪唑的用量的摩尔比为1:10:80;g-C3N4、Zn(NO3)2·6H2O的用量的质量比为1.07~1.08:1。
在根据本发明的一个实施方案中,步骤1)中,以g/mL计,g-C3N4的甲醇溶液的浓度为20-30%。
在根据本发明的一个实施方案中,步骤2)中,溶液B中Zn(NO3)2·6H2O的浓度为0.120~0.130mmol/mL,Fe(NO3)3·9H2O浓度为0.012~0.013mmol/mL。
在根据本发明的一个实施方案中,溶液C中二甲基咪唑的浓度为0.65~0.70mmol/mL。
在根据本发明的一个实施方案中,步骤6)中以5℃/min的升温速率梯度加热至550℃。
本发明进一步提供了根据上述的制备方法制备得到的Fe2O3-ZnO/g-C3N4复合材料。
本发明还提供了一种用于水中污染物光催化降解的组合物,所述组合物包含如上述的Fe2O3-ZnO/g-C3N4复合材料;
优选地,所述污染物选自双酚A、环丙沙星(CIP)、四环素(TC)、亚甲基蓝(MB)和对氯苯酚(4-CP)中的一种或多种。
本发明还提供了上述的Fe2O3-ZnO/g-C3N4复合材料或组合物在水净化处理中的应用;
优选地,所述应用为光催化降解水中的污染物,所述污染物选自双酚A、环丙沙星(CIP)、四环素(TC)、亚甲基蓝(MB)和对氯苯酚(4-CP)中的一种或多种;
优选地,所述污染物光催化降解是通过包括下述步骤的方法实现的:
将Fe2O3-ZnO/g-C3N4复合材料加入待处理水体中,使所述复合材料在待处理水体中的浓度为0.8~1.2g/L,搅拌混匀得到反应体系,然后将反应体系置于可见光照射下反应;优选地,于避光条件下搅拌至吸附-脱附平衡后得到反应体系;优选地,所述可见光光源为500W氙灯,更优选地,光催化反应时间不少于180min。
本发明具有以下有益效果:
1)本发明通过以氧化铁(Fe2O3)为电子桥梁,提供一种增强ZnO和g-C3N4界面连接,从而克服了晶体结构的障碍,提供了构建三元异质结光催化剂的合成方法;
2)本发明提供的Fe2O3-ZnO/g-C3N4复合材料在可见光条件下能够高效快速去除水中双酚A,并且其合成方法简单,有利于产业化生产,原料成本低廉。
3)复合材料在可见光条件下光催化降解水中双酚A效率高,且降解双酚A的产物不会产生二次污染。同时还具有广泛的pH适应性,对其他目标污染物(如CIP、TC和MB)同样具有良好的降解效果。
附图说明
图1为根据本发明的实施方案的合成路线图;
图2为不同材料的XRD图谱;
图3为不同材料的UV-vis DRS图谱;
图4为不同材料的禁带宽度Tauc曲线图;
图5为不同材料的N2吸附-脱附等温线图;
表1为不同材料的比表面积和孔结构图;
图6为不同材料的PL图谱;
图7为不同材料对双酚A的降解效果图;
图8为不同pH条件下复合材料对双酚A的降解效果图;
图9为复合材料对不同目标污染物的降解效果图。
具体实施方式
以下实施例用于说明本申请,但并非用来限制本申请的范围。
下面将更详细地描述本申请的具体实施例。提供这些实施例是为了能够更透彻地理解本申请,并且能够将本申请的范围完整的传达给本领域的技术人员。
如在通篇说明书及权利要求当中所提及的“包含”或“包括”为一开放式用语,故应解释成“包含但不限定于”。说明书后续描述为实施本申请的较佳实施方式,然所述描述乃以说明书的一般原则为目的,并非用以限定本申请的范围。本申请的保护范围当视所附权利要求所界定者为准。
如无特殊说明,本发明中所用到的试剂均可以商购途径购买得到。
实施例1 Fe2O3-ZnO/g-C3N4复合材料的制备
称取30g尿素,在空气氛围下以550℃煅烧,升温速率为5℃/min,煅烧4h。将煅烧产物用超声洗涤30min后再用去离子水洗涤三次,于70℃烘干备用。
将0.8g g-C3N4溶于30mL甲醇中,超声分散30min(记为溶液A)。将0.7437g Zn(NO3)2·6H2O和0.0101g Fe(NO3)3·9H2O共溶于20mL甲醇中(记为溶液B)。将1.642g二甲基咪唑溶于30mL甲醇中(记为溶液C)。
将溶液A和溶液B混合,搅拌均匀后再将溶液C缓慢滴加到混合溶液中,室温下搅拌2h,沉淀22h。将获得的沉淀以甲醇洗涤三次,70℃烘干备用。
将干燥后的材料均匀研磨后转移到管式加热炉中,空气氛围中以5℃/min的升温速率加热到550℃,煅烧2h获得Fe2O3-ZnO/g-C3N4复合材料。合成路线图如图1所示。
实施例2检测Fe2O3-ZnO/g-C3N4复合材料的结构和功能特征
对Fe2O3-ZnO/g-C3N4复合材料的结构进行XRD表征,结果如图2所示,Fe2O3-ZnO/g-C3N4复合材料的特征峰以g-C3N4为主,Fe2O3-ZnO的特征峰不明显,其原因是Fe2O3-ZnO含量较少导致。且图2中未出现其他特征峰,表明没有其他结晶相。
对Fe2O3-ZnO/g-C3N4复合材料进行UV-vis DRS表征,结果如图3所示,纯g-C3N4材料对光的吸收波长约为431nm,金属氧化物Fe2O3-ZnO的掺杂使g-C3N4的UV-vis DRS光谱的吸收边发生了红移,本发明提供的Fe2O3-ZnO/g-C3N4复合材料的吸收波长可达486nm。
此外,根据Tauc公式可得图4所示的不同材料的禁带宽度Tauc曲线图谱。由图4可以看出,g-C3N4和Fe2O3-ZnO/g-C3N4的带隙分别为3.05eV和2.83eV,表明本发明提供的复合材料具有增强的可见光响应能力。
对Fe2O3-ZnO/g-C3N4复合材料的比表面积进行表征,结果如图5所示,g-C3N4、Fe2O3-ZnO和Fe2O3-ZnO/g-C3N4均呈现出典型的Ⅳ型等温线并具有H3型滞后环,表明三种材料都具有介孔结构。经过计算,三种材料的BET和孔数值结果如表1所示,可见,本发明制备得到的Fe2O3-ZnO/g-C3N4的BET数值最大,说明其具有更大的比表面积,能够提供更多的吸附活性位点。
表1
对Fe2O3-ZnO/g-C3N4复合材料进行PL检测,结果如图6所示,Fe2O3-ZnO/g-C3N4的荧光发射强度显著减小,由此说明本发明提供的复合材料具有增强的载流子分离和运输能力,电子空穴对重新结合能力弱,光催化活性强。
实施例3光催化双酚A降解效果检测实验
将0.2g Fe2O3-ZnO/g-C3N4光催化剂加入到250mL浓度为10mg/L的双酚A溶液中,然后放入光催化反应器中。避光条件下磁力搅拌30min,使体系达到吸附-脱附平衡。然后将反应体系置于500W氙灯的照射下,进行可见光催化降解实验(反应时间为180min)。每反应30min取出2~3mL反应液,用0.22μm针式过滤器过滤。取样结束后将样品转移到液相小瓶中,放入冰箱冷藏保存待测,去除结果图7所示,催化剂投加量为0.2g时,g-C3N4对BPA的去除效率为43%,Fe2O3-ZnO对BPA的去除效率为12%,而Fe2O3-ZnO/g-C3N4对BPA的去除效率几乎可达100%,且达到完全去除的用时更少。由此可以看出Fe2O3-ZnO/g-C3N4复合催化剂在可见光条件下具有高效快速去除水中BPA的性能。
考察不同pH条件下Fe2O3-ZnO/g-C3N4催化剂对10mg/L双酚A的降解效果,结果如图8所示,本发明提供的Fe2O3-ZnO/g-C3N4复合材料具有较广的pH适应性,且在中性和弱酸性、弱碱性条件下均表现出更好的降解效果。
实施例4其它污染物的光催化降解效果检测
分别配制环丙沙星(CIP)、四环素(TC)、亚甲基蓝(MB)和对氯苯酚(4-CP)溶液进行降解实验,各污染物在溶液中浓度均为10mg/L,各污染物溶液体积分别为250mL,每种污染物溶液中均投入光催化剂Fe2O3-ZnO/g-C3N4 0.2g。
于避光条件下磁力搅拌30min,使体系达到吸附-脱附平衡。然后将反应体系置于500W氙灯的照射下,进行可见光催化降解实验(反应时间为180min)。每反应30min取出3~4mL反应液,以0.45μm针式过滤器过滤。取样结束后用紫外分光光度计进行浓度测定,降解结果如附9所示,本发明提供的Fe2O3-ZnO/g-C3N4对CIP的降解率为52%,对TC的降解率为57%,对MB的降解率为100%,对4-CP的降解率为18%。除4-CP外,Fe2O3-ZnO/g-C3N4对其他种类污染物也表现出较好的降解效果。
应注意的是,以上实例仅用于说明本发明的技术方案而非对其进行限制。尽管参照所给出的实例对本发明进行了详细说明,但是本领域的普通技术人员可根据需要对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的精神和范围。
Claims (10)
1.一种Fe2O3-ZnO/g-C3N4复合材料的制备方法,其特征在于,包括:
1)将g-C3N4分散于甲醇中,得到溶液A;
2)将Zn(NO3)2·6H2O和Fe(NO3)3·9H2O共溶于甲醇中,得溶液B;
3)将二甲基咪唑溶于甲醇中得到溶液C;
4)先将溶液A和溶液B混合均匀得到混合液,然后将溶液C缓慢滴加于混合液中,于室温下搅拌使均匀混合后沉淀,得到沉淀物;
5)将所述沉淀物以甲醇洗涤并干燥;
6)将干燥后的沉淀物均匀研磨后转移到管式加热炉,空气氛围中加热到550℃,煅烧即制备得至Fe2O3-ZnO/g-C3N4复合材料。
2.如权利要求1所述的制备方法,其特征在于,所述g-C3N4是通过包括下述步骤的方法制备得到的:将尿素于空气氛围中以550℃煅烧;然后将煅烧产物用超声洗涤30min后再以去离子水洗涤数次后烘干,即得g-C3N4;
优选地,以速率5℃/min梯度升温至550℃,煅烧4h。
3.如权利要求1所述的制备方法,其特征在于,Fe(NO3)3·9H2O、Zn(NO3)2·6H2O、二甲基咪唑的用量的摩尔比为1:10:80;g-C3N4、Zn(NO3)2·6H2O的用量的质量比为1.07~1.08:1。
4.如权利要求1所述的制备方法,其特征在于,步骤1)中,以g/mL计,g-C3N4的甲醇溶液的浓度为20-30%。
5.如权利要求1所述的制备方法,其特征在于,步骤2)中,溶液B中Zn(NO3)2·6H2O的浓度为0.120~0.130mmol/mL,Fe(NO3)3·9H2O浓度为0.012~0.013mmol/mL。
6.如权利要求1所述的制备方法,其特征在于,溶液C中二甲基咪唑的浓度为0.65~0.70mmol/mL。
7.如权利要求1所述的制备方法,其特征在于,步骤6)中以5℃/min的升温速率梯度加热至550℃。
8.根据权利要求1-7中任一项所述的制备方法制备得到的Fe2O3-ZnO/g-C3N4复合材料。
9.一种用于水中污染物光催化降解的组合物,其特征在于,所述组合物包含如权利要求8所述的Fe2O3-ZnO/g-C3N4复合材料;
优选地,所述污染物选自双酚A、环丙沙星(CIP)、四环素(TC)、亚甲基蓝(MB)和对氯苯酚(4-CP)中的一种或多种。
10.如权利要求8所述的Fe2O3-ZnO/g-C3N4复合材料或如权利要求9所述的组合物在水净化处理中的应用;
优选地,所述应用为光催化降解水中的污染物,所述污染物选自双酚A、环丙沙星(CIP)、四环素(TC)、亚甲基蓝(MB)和对氯苯酚(4-CP)中的一种或多种;
优选地,所述污染物光催化降解是通过包括下述步骤的方法实现的:
将Fe2O3-ZnO/g-C3N4复合材料加入到待处理水体中,使所述复合材料在待处理水体中的浓度为0.8~1.2g/L,搅拌混匀得到反应体系,然后将反应体系置于可见光照射下反应;优选地,于避光条件下搅拌至吸附-脱附平衡后得到反应体系;优选地,所述可见光光源为500W氙灯,更优选地,光催化反应时间不少于180min。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110635338.4A CN113457704B (zh) | 2021-06-08 | 2021-06-08 | 一种Fe2O3-ZnO/g-C3N4复合材料及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110635338.4A CN113457704B (zh) | 2021-06-08 | 2021-06-08 | 一种Fe2O3-ZnO/g-C3N4复合材料及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113457704A true CN113457704A (zh) | 2021-10-01 |
CN113457704B CN113457704B (zh) | 2023-08-18 |
Family
ID=77868713
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110635338.4A Active CN113457704B (zh) | 2021-06-08 | 2021-06-08 | 一种Fe2O3-ZnO/g-C3N4复合材料及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113457704B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114479357A (zh) * | 2022-03-21 | 2022-05-13 | 嘉兴学院 | 一种抗刮擦碳纤维环氧复合材料及其制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103736514A (zh) * | 2014-01-08 | 2014-04-23 | 阜阳师范学院 | 一种新颖的C3N4/ZnO/Fe2O3复合光催化剂的制备及应用 |
CN109701584A (zh) * | 2019-03-01 | 2019-05-03 | 华东交通大学 | 一种Z型光催化剂ZnO/Fe2O3/g-C3N4的制备方法及应用 |
-
2021
- 2021-06-08 CN CN202110635338.4A patent/CN113457704B/zh active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103736514A (zh) * | 2014-01-08 | 2014-04-23 | 阜阳师范学院 | 一种新颖的C3N4/ZnO/Fe2O3复合光催化剂的制备及应用 |
CN109701584A (zh) * | 2019-03-01 | 2019-05-03 | 华东交通大学 | 一种Z型光催化剂ZnO/Fe2O3/g-C3N4的制备方法及应用 |
Non-Patent Citations (1)
Title |
---|
NA MAO: ""investigating the Heteronjunction between ZnO/fe2O3 and g-C3N4 for an Enhanced Photocatalytic H2 Production under visible-light irradiation"" * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114479357A (zh) * | 2022-03-21 | 2022-05-13 | 嘉兴学院 | 一种抗刮擦碳纤维环氧复合材料及其制备方法 |
CN114479357B (zh) * | 2022-03-21 | 2023-08-01 | 嘉兴学院 | 一种抗刮擦碳纤维环氧复合材料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN113457704B (zh) | 2023-08-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106179444B (zh) | 一种活性炭负载碳掺杂石墨相氮化碳的制备方法 | |
Wang et al. | Hollow spherical WO3/TiO2 heterojunction for enhancing photocatalytic performance in visible-light | |
Obregón et al. | Heterostructured Er3+ doped BiVO4 with exceptional photocatalytic performance by cooperative electronic and luminescence sensitization mechanism | |
Chou et al. | Controlled hydrothermal synthesis of BiOxCly/BiOmBrn/g-C3N4 composites exhibiting visible-light photocatalytic activity | |
CN109395761A (zh) | 一种氮掺杂BiOIO3光催化剂的制备方法及其应用 | |
CN108607590A (zh) | g-C3N4嫁接卤氧化铋微球光催化剂的制备方法及应用 | |
CN109603881A (zh) | 改性碳量子点负载中空管状氮化碳光催化剂及其制备方法 | |
CN104525266A (zh) | 一种金属有机骨架材料光催化剂的制备方法与应用 | |
CN104525186A (zh) | 具有异质结构的球状钼酸铋纳米复合材料及其制备方法和应用 | |
CN111036265A (zh) | 一种复合纳米光催化剂CDs-N-BiOCl及其制备方法与应用 | |
Peng et al. | Rapid microwave-assisted solvothermal synthesis and visible-light-induced photocatalytic activity of Er3+-doped BiOI nanosheets | |
CN112892611A (zh) | 鱼鳞片管状氮化碳及其制备方法和应用 | |
CN108704658A (zh) | 一种氧化铋与碳化氮纳米片复合材料的制备方法 | |
CN101947463A (zh) | 一种高效紫外可见全光谱光催化材料的制备方法和应用 | |
Yin et al. | Synergistically enhanced photocatalytic degradation of tetracycline hydrochloride by Z-scheme heterojunction MT-BiVO4 microsphere/P-doped g-C3N4 nanosheet composite | |
CN102698784B (zh) | 一种可见光响应催化剂及其制备方法 | |
CN104383945A (zh) | 一种黑色溴氧化铋光催化剂及其制备方法 | |
CN105344379B (zh) | 一种水滑石负载酞菁铁可见光‑芬顿催化剂及其制备方法和应用 | |
Yang et al. | Dendritic BiVO 4 decorated with MnO x co-catalyst as an efficient hierarchical catalyst for photocatalytic ozonation | |
Nguyen et al. | Toward enhanced visible-light photocatalytic dye degradation and reusability of La3+ substituted ZnFe2O4 nanostructures | |
CN113457704B (zh) | 一种Fe2O3-ZnO/g-C3N4复合材料及其制备方法和应用 | |
CN113181943B (zh) | 一种MnO2复合g-C3N4材料及其制备方法和应用 | |
Zhang et al. | Synthesis, structural characterization and evaluation of a novel floating metal-free photocatalyst based on g-C3N4 grafted expanded perlite for the degradation of dyes | |
CN106975509A (zh) | 一种氮、铁共掺杂钒酸铋可见光催化剂的制备方法及应用 | |
Zhong et al. | Enhanced photocatalytic performance of Ga3+-doped ZnO |
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 |