CN113751032B - Preparation method and application of photodegradation catalyst for organic pollutants - Google Patents
Preparation method and application of photodegradation catalyst for organic pollutants Download PDFInfo
- Publication number
- CN113751032B CN113751032B CN202111187966.7A CN202111187966A CN113751032B CN 113751032 B CN113751032 B CN 113751032B CN 202111187966 A CN202111187966 A CN 202111187966A CN 113751032 B CN113751032 B CN 113751032B
- Authority
- CN
- China
- Prior art keywords
- niwo
- biox
- solution
- catalyst
- organic
- 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.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 51
- 238000001782 photodegradation Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 10
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 29
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical group [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 27
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 27
- 239000002244 precipitate Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000003760 magnetic stirring Methods 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- -1 halogen salt Chemical class 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 241000080590 Niso Species 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 150000001621 bismuth Chemical class 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 25
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 12
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 3
- 150000001875 compounds Chemical group 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 3
- 230000005540 biological transmission Effects 0.000 abstract 1
- 239000005416 organic matter Substances 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 23
- 239000010410 layer Substances 0.000 description 21
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 12
- 239000011734 sodium Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011941 photocatalyst Substances 0.000 description 8
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 229910006167 NiWO4 Inorganic materials 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 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 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000011206 ternary composite Substances 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 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 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 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 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- AXDJCCTWPBKUKL-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-imino-3-methylcyclohexa-2,5-dien-1-ylidene)methyl]aniline;hydron;chloride Chemical compound Cl.C1=CC(=N)C(C)=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 AXDJCCTWPBKUKL-UHFFFAOYSA-N 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229960002180 tetracycline Drugs 0.000 description 1
- 229930101283 tetracycline Natural products 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
-
- 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
- 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
- C02F2101/38—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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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
The invention discloses a preparation method and application of a photodegradation catalyst for organic pollutants, which belongs to the technical field of organic pollutant chemical treatment, and comprises the steps of firstly synthesizing NiWO with catalytic activity 4 Then synthesizing BiOX/NiWO under the hydrothermal reaction condition 4 (X=Cl, br, I) composite material, then wrapping Graphene Oxide (GO) on the surface of the composite material by a hydrothermal method to synthesize the super-strong photocatalytic composite material GO/BiOX/NiWO formed by compounding three materials 4 The method comprises the steps of carrying out a first treatment on the surface of the Synthesizing NiWO by the above compound sequence 4 A layered structure composite composed of BiOX and GO; the catalyst for photocatalytic degradation prepared by the method of the invention has NiWO in the inner layer 4 The method has the advantages that the method has a strong promotion effect on chemical bond breakage in the organic matter degradation process, the BiOX positioned on the secondary outer layer has a certain degree of photocatalytic activity, the graphene oxide positioned on the outermost layer has a strong photoelectron transmission capability and an organic pollutant adsorption capability, and the organic pollutants can be quickly adsorbed and removed through photodegradation by compounding the three materials.
Description
Technical Field
The invention relates to the technical field of organic pollutant chemical method treatment, in particular to a preparation method and application of a photodegradation catalyst for organic pollutants.
Background
With the rapid development of industry, various energy materials are consumed, and simultaneously a large amount of harmful substances are released to the environment, so that the environment and the ecological system are seriously damaged. The pollution of water resources is increasingly serious due to the discharge and deterioration of organic pollutants, so that the purification treatment of the organic pollutants in the water is not sustained, and the selection of a proper treatment mode is always a research hot spot.
Up to the present, numerous researchers have tried to remove organic pollutants from water bodies in various ways, such as adsorption, photocatalysis, ultrasound catalysis, fenton-like oxidation, etc., wherein the photocatalytic removal way is favored because the energy of solar radiation can be directly utilized in the degradation process. The most critical point in removing organic pollutants in water body by adopting the method is to select a proper, efficient and stable catalyst. The prior reported catalyst for photodegradation of organic pollutants mainly comprises TiO 2 ，BiVO 4 ，Bi 2 WO 6 ，Bi 2 O 3 ，Bi 2 O 2 CO 3 ，Bi 2 MoO 6 ，ZnO，C 3 N 4 BiOX (X=Cl, br, I) but is mostlyThe catalyst needs to be compounded with other materials to show higher catalytic performance. This is mainly caused by two factors, namely, the band gap energy of the material is relatively large, and photoelectrons cannot be effectively generated under the illumination condition; and secondly, the photoelectron and hole recombination rate is higher. Reducing the band gap width of the material by recombination with other materials while reducing the recombination rate of photoelectrons and holes is the core of research to improve the catalytic performance of the material.
Graphene oxide has excellent photoelectric characteristics, high carrier mobility and good chemical stability, and is widely applied to the synthesis process of a photocatalytic composite catalyst. Graphene oxide is a single-layer two-dimensional material which is honeycomb-shaped and is formed by connecting carbon atoms through chemical bonds, and is attached with hydroxyl groups and carboxyl groups. After other materials are compounded with the graphene oxide, hydroxyl groups in the structure have a remarkable improvement effect on degradation of organic pollutants, and in addition, the graphene oxide has strong carrier separation capability and high-efficiency mobility, can reduce the recombination rate of carriers, and shows strong electron receiving and transmitting characteristics.
NiWO 4 The composite has the characteristics of low price, small band gap, environment-friendly catalyst and the like, has the characteristics of proper band gap, high stability, high activity and intrinsic P-type semiconductor, and has certain photocatalytic performance on medicinal organic sewage. Such as V. Muthaj and its co-authors (Colloids surf. A, 567, 2019:43-54) to NiWO 4 With macromolecular semiconductor g-C 3 N 4 Nanosheet bonding to enhance NiWO 4 Photocatalytic activity under visible light. Furthermore, to improve NiWO 4 Mitra Mousavi and Aziz, haubi-Yangjeh (J. Mater. Sci., 53, 2018:9046-9063) were first synthesized to g-C by in situ co-precipitation 3 N 4 /Fe 3 O 4 Then nickel nitrate and sodium tungstate are used as raw materials in g-C 3 N 4 /Fe 3 O 4 NiWO is synthesized on the surface of (C) 4 And forming g-C by calcining 3 N 4 / Fe 3 O 4 /NiWO 4 It is catalytic to rhodamine B, methylene blue, methyl orange, fuchsin and phenolThe conversion activity was 12, 30, 52, 100,6 times higher than that of g-CN. Mahsa Pirhachemi and its co-authors (Sep. Purif. Technol., 193,2018:69-80) synthesized ZnO/NiWO with p-n-n heterojunction by a stepwise method 4 /Ag 2 CrO 4 Nanocomposite, wherein when Ag 2 CrO 4 When the mass ratio is 30%, the rhodamine B has the highest photodegradation efficiency. In conclusion, niWO 4 Only heterojunction with other compounds can show higher catalytic activity on organic photodegradation.
BiOX（X=Cl，Br，I），NiWO 4 And graphene oxide has a certain degree of photocatalytic activity, but when the graphene oxide is used alone to catalyze photodegradation of organic pollutants, the effect is poor, and the industrial requirements cannot be met. The invention synthesizes a material with super-strong photocatalytic degradation and removal of organic pollutants based on the previous study for the first time, which is prepared by NiWO 4 The three-layer photocatalyst is characterized in that the photocatalyst is an inner layer, a secondary outer layer is BiOX, the outermost layer is a three-layer structure photocatalyst of graphene oxide, the outer layer GO can efficiently absorb electrons and transfer the electrons to the inner layer structure, meanwhile, the graphene oxide of the outer layer has adsorption and capture capacity on organic pollution, and the NiWO of the innermost layer 4 Has stronger bond breaking effect on organic matters. By design of synthesized GO/BiOX/NiWO 4 (X=Cl, br, I) gathers the advantage of multiple materials, has superstrong photocatalytic degradation to organic pollutant
Disclosure of Invention
In order to solve the problems of low activity, low catalytic efficiency and the like of the organic pollutant degradation material in the prior art, the invention provides a preparation method and application of an organic pollutant photodegradation catalyst with a three-layer structure; the invention synthesizes with NiWO 4 The catalyst synthesized by the preparation method provided by the invention has higher catalytic activity and recycling performance in the photodegradation of organic pollutants.
In order to achieve the above purpose, the invention is implemented according to the following technical scheme:
the preparation method of the photodegradation catalyst for organic pollutants comprises the following steps:
step1, synthesis of NiWO 4 ；
Step1.1, dissolving tungstate in deionized water to enable the mass concentration to be between 0.1 and 10g/L, and marking the solution as A;
step1.2, dissolving nickel salt with the same molar weight as tungstate in ionized water to ensure that the mass concentration is between 0.1 and 10g/L, and marking the solution as solution B;
step1.3, heating the solution A to 30-80 ℃ under magnetic stirring, dripping the solution B into the solution A, and continuously stirring for 6-48 hours;
step1.4, filtering, washing the precipitate for 3-5 times after stirring is finished, drying at 60-90 ℃ for 10-24 h, calcining the dried sample at 400-700 ℃ for 3-6 h to obtain NiWO 4 ；
Step2, synthesis of BiOX/NiWO 4 : niWO obtained from Step1.4 4 Dispersing in a mixed solution of an organic solvent and deionized water to enable the mass solubility to be between 0.1 and 10g/L, adding halogen salt into the uniformly dispersed solution, stirring for 0.5 to 3 hours, adding bismuth salt with the same molar quantity as the halogen salt, continuously stirring for 0.5 to 3 hours, and then transferring the solution into a hydrothermal reaction kettle for crystallization at 120 to 180 ℃ for 12 to 48 hours; after the reaction is finished, centrifuging to obtain a precipitate, washing the precipitate with deionized water for 3-5 times, and drying the precipitate at 60-90 ℃ for 10-24 hours to obtain the composite material BiOX/NiWO 4 ；
Step3, preparation of GO/BiOX/NiWO 4 : biOX/NiWO prepared from Step2 4 Dispersing in organic solvent, adding graphene oxide obtained by freeze drying by Hummers method, wherein the graphene oxide mass ratio is BiOX/NiWO 4 1-40% of the weight; stirring for 0.5-10 h under magnetic stirring, transferring the mixed solution into a reaction kettle, crystallizing for 12-48 h at 120-180 ℃ to finally obtain GO/BiOX/NiWO 4 。
Specifically, the tungstate in Step1.1 is Li 2 WO 4 、Na 2 WO 4 、K 2 WO 4 、（NH 4 ） 2 WO 4 One or more of the following;
specifically, the nickel salt of Step1.2 is Ni(NO 3 ) 2 、NiCl 2 、(HCOO) 2 Ni、(CHCOO) 2 Ni、NiSO 4 One or more of the following;
specifically, the halogen salt in Step2 is one or more of KCl, KBr, KI, naCl, naBr, naI, liCl, liBr, liI;
specifically, the organic solvent in Step2 and Step3 is one or more of methanol, ethanol, acetonitrile, dimethylformamide, dimethylacetamide, tetrahydrofuran and 1, 4-dioxane;
specifically, the addition amount of the halogen salt in Step2 is NiWO 4 1-100% of the molar amount;
specifically, the volume ratio of the organic solvent to the deionized water mixed solution in Step3 is 0.1-0.9;
the application of the catalyst prepared by the preparation method of the organic pollutant photodegradation catalyst is that the organic pollutant photodegradation catalyst can promote the photodegradation of organic pollutants, and the organic pollutants are one or more of rhodamine B, methylene blue, methyl orange, phenol, bisphenol A, tetracycline and antibiotics.
Compared with the prior art, the preparation method of the photodegradation catalyst for organic pollutants has the following beneficial effects:
the photodegradation catalyst for organic pollutants prepared by the method of the invention is prepared by NiWO 4 Is a laminated structure formed by superposing three layers of substances, wherein the BiOX (X=Cl, br, I) is a secondary outer layer and the GO is an outermost layer, and the NiWO of the inner layer 4 The organic pollutant chemical bond has a strong breaking effect, the BiOX of the secondary outer layer can promote photocatalytic degradation of the organic pollutant, the GO of the outermost layer has a strong adsorption effect on the organic pollutant, and in addition, the GO has a strong conductivity and promotes photoelectron generation. Synthesized GO/BiOX/NiWO with three-layer structure 4 The GO of the outer layer adsorbs the organic pollutant on the surface, and then passes through the secondary outer layer BiOX and the innermost layer NiWO 4 Is photodegradation.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 shows BiOI/NiWO 4 A comparison chart of the relationship between the degradation rate of the composite catalyst to methylene blue and the change of the degradation rate of the composite catalyst to methylene blue with time;
FIG. 2 is a schematic view ofn%GO/BiOI/NiWO4(n=1, 10, 20) a comparison graph of degradation rate of ternary composite catalyst to methylene blue over time;
FIG. 3 is a graph comparing degradation rates of a 20% GO/BiOX/NiWO4 (X=Cl, br, I) ternary composite catalyst to methylene blue over time;
FIG. 4 is a diagram of BiOI/NiWO 4 With 20% GO/BiOI/NiWO 4 And (3) comparing the relation of the degradation rate of the composite catalyst to methylene blue with time.
Detailed Description
The invention will be further described with reference to the accompanying drawings and specific embodiments, wherein the exemplary embodiments and descriptions of the invention are for purposes of illustration, but are not intended to be limiting.
Comparative example 1, preparation of NiWO 4 The catalyst comprises the following steps:
na of handle 2 WO 4 Dissolved in a volume of deionized water to a mass concentration of 1.0g/L, designated as solution A. Handle and Na 2 WO 4 Equimolar amount of NiCl 2 6H 2 O was dissolved in a volume of ionized water to a mass concentration of 1.0/L, designated as liquid B. Under magnetic stirring, the solution A is heated to 30 ℃, the solution B is added into the solution A in a dropwise manner, and stirring is continued for 6 hours. After stirring, filtering and washing the precipitate for 3 times, drying at 60 ℃ for 12 hours, calcining the dried sample at 600 ℃ for 3 hours to obtain NiWO 4 。
Comparative example 2 preparation of BiOCl/NiWO 4 The photodegradation catalyst comprises the following steps:
1) Na of handle 2 WO 4 Dissolved in a volume of deionized water to a mass concentration of 1.0g/L, designated as solution A. Handle and Na 2 WO 4 Equimolar amount of NiCl 2 6H 2 O was dissolved in a volume of ionized water to a mass concentration of 1.0/L, designated as liquid B. Under magnetic stirring, the solution A is heated to 30 ℃, the solution B is added into the solution A in a dropwise manner, and stirring is continued for 6 hours. After stirring, filtering and washing the precipitate for 3 times, drying at 60 ℃ for 12 hours, calcining the dried sample at 600 ℃ for 3 hours to obtain NiWO 4 。
2) Obtaining NiWO from step1 4 Dispersing in a certain volume of mixed solution of dimethylformamide and deionized water to make the mass solubility be 1.0g/L, and adding NiWO into the uniformly dispersed solution 4 Equimolar amount of KCl, stirring for 0.5h, adding Bi (NO) equimolar to KBr 3 ) 3 Stirring is continued for 0.5h, and then the solution is transferred into a hydrothermal reaction kettle for crystallization at 120 ℃ for 12h. After the reaction is finished, centrifuging to obtain a precipitate, washing the precipitate with deionized water for 3 times, and drying the precipitate at 60 ℃ for 12 hours to obtain the composite material BiOCl/NiWO 4 。
Comparative example 3 preparation of BiOBr/NiWO 4 The photodegradation catalyst comprises the following steps:
1) Na of handle 2 WO 4 Dissolved in a volume of deionized water to a mass concentration of 1.0g/L, designated as solution A. Handle and Na 2 WO 4 Equimolar amount of NiCl 2 6H 2 O was dissolved in a volume of ionized water to a mass concentration of 1.0/L, designated as liquid B. Under magnetic stirring, the solution A is heated to 30 ℃, the solution B is added into the solution A in a dropwise manner, and stirring is continued for 6 hours. After stirring, filtering and washing the precipitate for 3 times, drying at 60 ℃ for 12 hours, calcining the dried sample at 600 ℃ for 3 hours to obtain NiWO 4 。
2) Obtaining NiWO from step1 4 Dispersing in a certain volume of mixed solution of methanol and deionized water to make the mass solubility be 1.0g/L, and adding NiWO and the solution uniformly dispersed 4 Equimolar amount of KBr, stirring for 0.5h, adding Bi (NO) 3 ) 3 Stirring for 0.5 hr, transferring the solution into hydrothermal reactor, crystallizing at 120deg.CAnd (5) carrying out chemical treatment for 12h. After the reaction is finished, centrifuging to obtain a precipitate, washing the precipitate with deionized water for 3 times, and drying the precipitate at 60 ℃ for 12 hours to obtain the composite material BiOBr/NiWO 4 。
Comparative example 4 preparation of a BiOI/NiWO4 photodegradation catalyst the procedure was as follows:
1) Na of handle 2 WO 4 Dissolved in a volume of deionized water to a mass concentration of 1.0g/L, designated as solution A. Handle and Na 2 WO 4 Equimolar amount of NiCl 2 6H 2 O was dissolved in a volume of ionized water to a mass concentration of 1.0/L, designated as liquid B. Under magnetic stirring, the solution A is heated to 30 ℃, the solution B is added into the solution A in a dropwise manner, and stirring is continued for 6 hours. After stirring, filtering and washing the precipitate for 3 times, drying at 60 ℃ for 12 hours, calcining the dried sample at 600 ℃ for 3 hours to obtain NiWO 4 。
2) Obtaining NiWO from step1 4 Dispersing in a certain volume of mixed solution of dimethylformamide and deionized water to make the mass solubility be 1.0g/L, and adding NiWO into the uniformly dispersed solution 4 Equimolar amount of KI, stirring for 0.5h, adding Bi (NO) in equimolar amount with KI 3 ) 3 Stirring is continued for 0.5h, and then the solution is transferred into a hydrothermal reaction kettle for crystallization at 120 ℃ for 12h. After the reaction is finished, centrifuging to obtain a precipitate, washing the precipitate with deionized water for 3 times, and drying the precipitate at 60 ℃ for 12 hours to obtain the composite material BiOI/NiWO 4 。
The activity of the catalyst in comparative examples 1 to 4 was investigated with photocatalytic degradation of methylene blue as an evaluation criterion, and the catalytic reaction was carried out as follows: 20mL of methylene blue solution (100 mg/L) is measured and diluted to 100mL, 30mg of the catalyst prepared above is added into the solution, the solution is placed in a dark environment for 30min under magnetic stirring, then the solution is moved to a xenon lamp light source (MICROSALAR 300) under the magnetic stirring, the reaction is continued for 180min under the action of magnetic stirring, samples are taken every 30min in the reaction process, and a filter membrane of 0.22um is used for filtering the solution after each sampling. The filtered solution is detected by an ultraviolet-visible spectrophotometer, and the photodegradation rate of the organic pollutants is calculated according to the drawn standard curve. Under the same experimental conditions, the light source of a xenon lamp irradiates for 180min, and the NiWO 4 With BiOCl/NiWO 4 The degradation rate of the methylene blue is 74.20 percent and 80.19 percent respectively; under the same experimental conditions, the light source of a xenon lamp irradiates for 180min, and the NiWO 4 With BiOCl/NiWO 4 The degradation rate of the methylene blue is 74.20 percent and 84.21 percent respectively; as shown in FIG. 1, under the same experimental conditions, the NiWO was irradiated by a xenon lamp light source for 180min 4 With BiOCl/NiWO 4 The degradation rate of the methylene blue is 74.20 percent and 86.35 percent respectively.
Example 1 preparation of GO/BiOCl/NiWO 4 Photodegradation catalyst
1) Na of handle 2 WO 4 Dissolved in a volume of deionized water to a mass concentration of 1.0g/L, designated as solution A. Handle and Na 2 WO 4 Equimolar amount of NiCl 2 6H 2 O was dissolved in a volume of ionized water to a mass concentration of 1.0/L, designated as liquid B. Under magnetic stirring, the solution A is heated to 30 ℃, the solution B is added into the solution A in a dropwise manner, and stirring is continued for 6 hours. After stirring, filtering and washing the precipitate for 3 times, drying at 60 ℃ for 12 hours, calcining the dried sample at 600 ℃ for 3 hours to obtain NiWO 4 。
2) Obtaining NiWO from step1 4 Dispersing into a certain volume of dimethylformamide and deionized water to make the mass solubility be within 1.0g/L, then adding NiWO into the uniformly dispersed solution 4 Equimolar amount of KCl, stirring for 0.5h, adding Bi (NO) in equimolar amount with KCl 3 ) 3 Stirring is continued for 0.5h, and then the solution is transferred into a hydrothermal reaction kettle for crystallization at 120 ℃ for 12h. After the reaction is finished, centrifuging to obtain a precipitate, washing the precipitate with deionized water for 3 times, and drying the precipitate at 60 ℃ for 12 hours to obtain the composite material BiOCl/NiWO 4 。
3) BiOCl/NiWO prepared in step2 4 Dispersing in methanol, adding lyophilized Graphene Oxide (GO) prepared by Hummers method, and mixing with a mass ratio of BiOCl/NiWO 4 20% of the mass. Stirring for 0.5h under magnetic stirring, transferring the mixed solution into a reaction kettle, crystallizing at 120 ℃ for 12h, and finally obtaining the ultra-strong light catalytic composite material 20% GO/BiOCl/NiWO 4 。
The photocatalytic degradation of methylene blue was used as an evaluation criterion in example 1The activity of the catalyst was studied and the catalytic reaction was carried out as follows: 20mL of methylene blue solution (100 mg/L) is measured and diluted to 100mL, 30mg of the catalyst prepared above is added into the solution, the solution is placed in a dark environment for 30min under magnetic stirring, then the solution is moved to a xenon lamp light source (MICROSALAR 300) under the magnetic stirring, the reaction is continued for 180min under the action of magnetic stirring, samples are taken every 30min in the reaction process, and a filter membrane of 0.22um is used for filtering the solution after each sampling. The filtered solution is detected by an ultraviolet-visible spectrophotometer, and the photodegradation rate of the organic pollutants is calculated according to the drawn standard curve. As shown in FIG. 3, the degradation rate of methylene blue by 90min of reaction was 99.91%. Compared with comparative example 2, 20% GO/BiOCl/NiWO 4 Ratio BiOCl/NiWO 4 The catalyst has higher catalytic performance on methylene blue degradation, and the degradation rate of the catalyst is 39.57% higher than that of the catalyst when the reaction is carried out for 90min under the same catalytic condition.
EXAMPLE 2,
The preparation procedure and method were the same as in example 1, except that KCl in step 2) of example 1 was changed to KBr.
The samples prepared in example 2 were subjected to photocatalyst performance test, and the specific procedure was the same as in example 1. As shown in FIG. 3, after 90 minutes of reaction, the degradation rate of methylene blue was 99.93%. Compared with comparative example 3, 20% GO/BiOBr/NiWO 4 Ratio BiOBr/NiWO 4 The catalyst has higher catalytic performance on methylene blue degradation, and the degradation rate of the catalyst is 35.37% higher than that of the catalyst when the reaction is carried out for 90min under the same catalytic condition.
EXAMPLE 3,
The preparation procedure and method were the same as in example 1, except that KCl in step 2) of example 1 was changed to KI.
The samples prepared in example 3 were subjected to photocatalyst performance test, and the specific procedure was the same as in example 1. After 90min of reaction, the degradation rate of methylene blue was 99.82% (see FIG. 3). Compared with comparative example 4, 20% GO/BiOI/NiWO 4 Ratio BiOI/NiWO 4 The catalyst has higher catalytic performance on methylene blue degradation, and under the same catalytic condition, as shown in fig. 4, the degradation rate of the catalyst is 30.26% higher than that of the catalyst when the reaction is carried out for 90 min.
EXAMPLE 4,
The preparation procedure and method were the same as in example 3.
The activity of the catalyst in example 1 was studied using photocatalytic degradation of methylene blue as an evaluation criterion, and the catalytic reaction was carried out as follows: 20mL of methylene blue solution (100 mg/L) is measured and diluted to 100mL, 10mg of the catalyst prepared above is added into the solution, the solution is placed in a dark environment for 30min under magnetic stirring, then the solution is moved to a xenon lamp light source (MICROSALAR 300) under the magnetic stirring, the reaction is continued for 180min under the action of magnetic stirring, samples are taken every 30min in the reaction process, and a filter membrane of 0.22um is used for filtering the solution after each sampling. The filtered solution is detected by an ultraviolet-visible spectrophotometer, and the photodegradation rate of the organic pollutants is calculated according to the drawn standard curve. The 180min back should be 91.12%.
EXAMPLE 5,
The preparation procedure and method were the same as in example 4, except that the mass ratio of Graphene Oxide (GO) in step 3) of example 1 was adjusted to 1%.
The samples prepared in example 5 were subjected to photocatalyst performance test, and the specific procedure was the same as in example 1. After 180min of reaction, the degradation rate of methylene blue was 88.64%, as shown in FIG. 2.
EXAMPLE 6,
The preparation procedure and method were the same as in example 4, except that the mass ratio of Graphene Oxide (GO) in step 3) of example 1 was adjusted to 10%.
The samples prepared in example 5 were subjected to photocatalyst performance test, and the specific procedure was the same as in example 1. After 180min of reaction, the degradation rate of methylene blue was 98.09%, as shown in FIG. 2.
From the data analysis of the above comparative examples and examples, it is known to use BiOX (X=Cl, br, I) and NiWO 4 After compounding, biOX/NiWO 4 Ratio NiWO 4 The photodegradation rate of methylene blue is improved to a certain extent, but the improvement range is not large. For BiOX/NiWO 4 After reintroduction of graphene oxide into the structure of (C) GO/BiOX/NiWO 4 The photodegradation rate of the methylene blue is larger than that before the graphene oxide is introducedIs improved. With the increase of the content of the graphene oxide, the catalytic activity is obviously enhanced, and the promotion of the catalytic effect is not obvious after the content of the graphene oxide exceeds a certain proportion. The graphene oxide has strong adsorption capacity and strong photo-electronic generation capacity on organic pollutants, and the GO is increased in a low content state, so that the adsorption on the organic pollutants can be improved, more photoelectrons can be promoted, and the degradation on active sites of an inner layer after the adsorption of the organic pollutants is promoted; when the content of GO exceeds a certain content, the content of GO is increased to reduce the active ingredients with the function of taking off and degrading in the catalyst, so that a large amount of organic pollutants are adsorbed on the surface of the catalyst, and the degradation capability is reduced. In conclusion, for the synthesized ternary composite photocatalyst, reasonable doping of the graphite oxide amount is beneficial to regulation and control of synthesis of the catalyst with high catalytic activity for degrading organic pollutants.
The catalyst synthesized by the technical proposal provided by the patent gathers NiWO 4 The advantages of graphene oxide and BiOX (X=Cl, br, I) are that the catalyst has higher catalytic activity on degrading organic pollutants.
The technical scheme of the invention is not limited to the specific embodiment, and all technical modifications made according to the technical scheme of the invention fall within the protection scope of the invention.
Claims (6)
1. The application of the organic pollutant photodegradation catalyst is characterized in that the organic pollutant photodegradation catalyst is prepared by using NiWO 4 The composite material is a layered structure formed by superposing three layers of substances, namely an inner layer, a BiOX layer as a secondary outer layer and a GO layer as an outermost layer; x in the BiOX is one of Cl, br and I;
the organic pollutant photodegradation catalyst can promote photodegradation of organic pollutants; the organic pollutant is methylene blue;
the preparation of the organic pollutant photodegradation catalyst comprises the following steps:
step1, synthesis of NiWO 4 ；
Step1.1, dissolving tungstate in deionized water to enable the mass concentration to be between 0.1 and 10g/L, and marking the solution as A;
step1.2, dissolving nickel salt with the same molar weight as tungstate in deionized water to ensure that the mass concentration is between 0.1 and 10g/L, and marking the solution as solution B;
step1.3, heating the solution A to 30-80 ℃ under magnetic stirring, dripping the solution B into the solution A, and continuously stirring for 6-48 hours;
step1.4, filtering, washing the precipitate for 3-5 times after stirring is finished, drying at 60-90 ℃ for 10-24 h, calcining the dried sample at 400-700 ℃ for 3-6 h to obtain NiWO 4 ；
Step2, synthesis of BiOX/NiWO 4 : niWO obtained from Step1.4 4 Dispersing in a mixed solution of an organic solvent and deionized water to enable the mass concentration to be between 0.1 and 10g/L, adding halogen salt into the uniformly dispersed solution, stirring for 0.5 to 3 hours, adding bismuth salt with the same molar quantity as the halogen salt, continuously stirring for 0.5 to 3 hours, transferring the solution into a hydrothermal reaction kettle, and crystallizing at 120 to 180 ℃ for 12 to 48 hours; after the reaction is finished, centrifuging to obtain a precipitate, washing the precipitate with deionized water for 3-5 times, and drying the precipitate at 60-90 ℃ for 10-24 hours to obtain the composite material BiOX/NiWO 4 ；
Step3, preparation of GO/BiOX/NiWO 4 : biOX/NiWO prepared from Step2 4 Dispersing in organic solvent, adding graphene oxide obtained by freeze drying by Hummers method, wherein the graphene oxide mass ratio is BiOX/NiWO 4 20-40% of the weight; stirring for 0.5-10 h under magnetic stirring, transferring the mixed solution into a reaction kettle, crystallizing for 12-48 h at 120-180 ℃ to finally obtain GO/BiOX/NiWO 4 。
2. The use of the photodegradation catalyst for organic pollutants according to claim 1, wherein the tungstate in step1.1 is Li 2 WO 4 、Na 2 WO 4 、K 2 WO 4 、（NH 4 ） 2 WO 4 One or more of them.
3. The use of the photodegradation catalyst for organic pollutants according to claim 1, wherein the nickel salt of step1.2 is Ni (NO 3 ) 2 、NiCl 2 、(HCOO) 2 Ni、(CHCOO) 2 Ni、NiSO 4 One or more of them.
4. The use of the photodegradation catalyst for organic pollutants according to claim 1, wherein the halogen salt in Step2 is one or more of KCl, KBr, KI, naCl, naBr, naI, liCl, liBr, liI.
5. The application of the organic pollutant photodegradation catalyst according to claim 1, wherein the organic solvent in Step2 and Step3 is one or more of methanol, ethanol, acetonitrile, dimethylformamide, dimethylacetamide, tetrahydrofuran and 1, 4-dioxane.
6. The use of the photodegradation catalyst for organic pollutants according to claim 1, wherein the addition amount of halogen salt in Step2 is NiWO 4 1-100% of the molar quantity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111187966.7A CN113751032B (en) | 2021-10-12 | 2021-10-12 | Preparation method and application of photodegradation catalyst for organic pollutants |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111187966.7A CN113751032B (en) | 2021-10-12 | 2021-10-12 | Preparation method and application of photodegradation catalyst for organic pollutants |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113751032A CN113751032A (en) | 2021-12-07 |
| CN113751032B true CN113751032B (en) | 2023-12-15 |
Family
ID=78799254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111187966.7A Active CN113751032B (en) | 2021-10-12 | 2021-10-12 | Preparation method and application of photodegradation catalyst for organic pollutants |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113751032B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116477669A (en) * | 2022-01-15 | 2023-07-25 | 长安大学 | Amorphous nano catalyst, preparation method and application thereof |
| CN114849762B (en) * | 2022-06-14 | 2024-02-06 | 蚌埠学院 | g-C for degrading lipophilic azonaphthalene compound 3 N 4 /BiOI/Ag 2 CrO 4 Preparation method and application of ternary heterojunction photocatalyst |
| CN115007171B (en) * | 2022-07-22 | 2024-03-19 | 江西理工大学 | Preparation method of methanol oxidation catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110918104A (en) * | 2019-11-22 | 2020-03-27 | 西北矿冶研究院 | Ternary heterojunction graphene-bismuth oxide/bismuth oxyhalide visible light photocatalyst and preparation method thereof |
| CN111974417A (en) * | 2020-09-18 | 2020-11-24 | 常州大学 | Cadmium sulfide/nickel tungstate composite visible-light-driven photocatalyst, preparation method and application |
-
2021
- 2021-10-12 CN CN202111187966.7A patent/CN113751032B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110918104A (en) * | 2019-11-22 | 2020-03-27 | 西北矿冶研究院 | Ternary heterojunction graphene-bismuth oxide/bismuth oxyhalide visible light photocatalyst and preparation method thereof |
| CN111974417A (en) * | 2020-09-18 | 2020-11-24 | 常州大学 | Cadmium sulfide/nickel tungstate composite visible-light-driven photocatalyst, preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| BiOBr/GO复合纳米光催化剂的制备及可见光下降解环丙沙星废水;郑乐媚;关亦玮;文定;唐叶如;李旭辉;令玉林;周建红;;环境化学;39(08);第2137-2146页 * |
| Enhanced visible-light photocatalytic activity of ZnS/BiOBr/graphene oxide ternary composite;Wenjun Zhang等;Journal of Physics and Chemistry of Solids;第127卷;第19-27页 * |
| Spherical NiWO4-reduced graphene oxide nanocomposite for effective visible light driven photocatalytic activity for the decolourisation of organic pollutants;Sathish Mohan Botsa等;Arabian Journal of Chemistry;第13卷(第11期);第8489-8497页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113751032A (en) | 2021-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113751032B (en) | Preparation method and application of photodegradation catalyst for organic pollutants | |
| Zhang et al. | Enhanced photocatalytic performance and degradation pathway of Rhodamine B over hierarchical double-shelled zinc nickel oxide hollow sphere heterojunction | |
| Chen et al. | Synergy effect between adsorption and heterogeneous photo-Fenton-like catalysis on LaFeO3/lignin-biochar composites for high efficiency degradation of ofloxacin under visible light | |
| CN106824213B (en) | Cobalt oxide doped bismuth subcarbonate/bismuth oxychloride photocatalyst and preparation method thereof | |
| CN108927176B (en) | Copper sulfide/bismuth vanadate heterojunction photocatalyst and preparation method thereof | |
| CN109622013B (en) | Graphite-like carbon nitride- (110) crystal face bismuth vanadate Z-type heterojunction photocatalyst and preparation method and application thereof | |
| CN108816265B (en) | Bismuth vanadate/nitrogen-doped carbon quantum dot/cuprous oxide double-Z-type photocatalyst and preparation method and application thereof | |
| CN110639563B (en) | Bismuth oxychloride/silver ferrite ternary composite Z-type photocatalyst and preparation method and application thereof | |
| CN110227453B (en) | Preparation method of AgCl/ZnO/GO composite visible light catalyst | |
| Raja et al. | Direct Z-scheme ZnIn2S4 spheres and CeO2 nanorods decorated on reduced-graphene-oxide heterojunction photocatalysts for hydrogen evolution and photocatalytic degradation | |
| CN113070084B (en) | Ternary composite material based on graphite phase carbon nitride and preparation method and application thereof | |
| Nsib et al. | Effect of some operational parameters on the hydrogen generation efficiency of Ni-ZnO/PANI composite under visible-light irradiation | |
| CN111437856A (en) | Bismuth oxyhalide/g-C3N4Preparation of heterojunction photocatalyst | |
| CN114433137B (en) | Bismuth/bismuth oxychloride microsphere photocatalyst and preparation method and application thereof | |
| Zhu et al. | Novel Cu-Fe/LDH@ BiOI1. 5 photocatalyst effectively degrades tetracycline under visible light irradiation | |
| Luo et al. | Preparation and characterization of Bi12TiO20/RGO as high-efficiency photocatalysts for degradation of dye wastewater | |
| CN111974374A (en) | Preparation method of biochar modified nano ZnO composite powder | |
| CN110302826B (en) | Basic bismuth nitrate and bismuth oxyiodide composite photocatalyst and preparation method and application thereof | |
| CN101708454B (en) | Flaky Mg-Al composite oxide for loading ZnO nano particles as well as preparation and application thereof | |
| Liu et al. | Current status of research on BiOX-based heterojunction photocatalytic systems: Synthesis methods, photocatalytic applications and prospects | |
| CN112316950B (en) | Load type TiO 2 Catalyst, preparation method and application thereof | |
| Dong et al. | Synthesis of Tb-doped ZnO/RGO nanocomposites and its enhanced photocatalytic activity under visible light irradiation | |
| CN110743575A (en) | AgIn with adsorption-photocatalysis synergistic effect5S8/SnS2Method for preparing solid solution catalyst | |
| CN113856703A (en) | Indium zinc sulfide and bismuth molybdate nanosheet composite photocatalyst with nanoflower structure and preparation method and application thereof | |
| CN110586149B (en) | Bismuth molybdate/titanium carbide heterojunction two-dimensional photocatalytic material and preparation method and application thereof |
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 |