CN112588302B - alpha-MnO-containing 2 Photocatalytic system, preparation method and application thereof - Google Patents
alpha-MnO-containing 2 Photocatalytic system, preparation method and application thereof Download PDFInfo
- Publication number
- CN112588302B CN112588302B CN202011527438.7A CN202011527438A CN112588302B CN 112588302 B CN112588302 B CN 112588302B CN 202011527438 A CN202011527438 A CN 202011527438A CN 112588302 B CN112588302 B CN 112588302B
- Authority
- CN
- China
- Prior art keywords
- mno
- alpha
- nahso
- mixed slurry
- photocatalytic
- 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
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011268 mixed slurry Substances 0.000 claims abstract description 24
- 230000015556 catabolic process Effects 0.000 claims abstract description 16
- 238000006731 degradation reaction Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 230000000694 effects Effects 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 9
- 239000010935 stainless steel Substances 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000002351 wastewater Substances 0.000 claims description 25
- 239000012265 solid product Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 10
- 239000005416 organic matter Substances 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 6
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 6
- 229940012189 methyl orange Drugs 0.000 claims 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 claims description 6
- 229940043267 rhodamine b Drugs 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000004098 Tetracycline Substances 0.000 claims 1
- 229960002180 tetracycline Drugs 0.000 claims 1
- 229930101283 tetracycline Natural products 0.000 claims 1
- 235000019364 tetracycline Nutrition 0.000 claims 1
- 150000003522 tetracyclines Chemical class 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 11
- 239000011941 photocatalyst Substances 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 6
- 238000003756 stirring Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 24
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000002070 nanowire Substances 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000001782 photodegradation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 241001070941 Castanea Species 0.000 description 1
- 235000014036 Castanea Nutrition 0.000 description 1
- 241000245665 Taraxacum Species 0.000 description 1
- 235000005187 Taraxacum officinale ssp. officinale Nutrition 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- 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
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention provides a composition containing alpha-MnO 2 Belonging to the technical field of photocatalysts. The photocatalytic system comprises alpha-MnO 2 And NaHSO 4 ，NaHSO 4 And alpha-MnO 2 The mass ratio of (A) to (B) is 0.05-1; alpha-MnO 2 The preparation method comprises the following steps: mixing KMnO 4 Dissolving in deionized water, and adding MnSO dropwise under stirring 4 ·H 2 In the water solution of O to obtain mixed slurry, transferring the mixed slurry into a stainless steel autoclave with a polytetrafluoroethylene lining, and preserving the heat for 10-13h at the temperature of 130-145 ℃ in an oven; cooling the mixed slurry, carrying out suction filtration and washing, drying the obtained product in an oven, calcining the dried product in a muffle furnace at 280-320 ℃ in the air atmosphere for 1.5-2.5h to obtain alpha-MnO 2 . The invention has higher photocatalysis efficiency, obvious degradation effect on various organic matters, high degradation efficiency and simple system operation.
Description
Technical Field
The invention relates to a photocatalytic degradation treatment technology of organic matter wastewater, relates to the technical field of photocatalysts, and particularly relates to a photocatalyst containing alpha-MnO 2 The photocatalytic system, a preparation method and an application thereof.
Background
In industrial processes, a large amount of organic waste water is discharged, and organic substances in the organic waste water exist in a water system in a suspended or dissolved state and are difficult to degrade. Most organic matters are toxic and harmful, cause harm to other organisms in the water body, can be continuously degraded under the action of microorganisms and other organisms, but oxygen needs to be consumed in the decomposition process, the dissolved oxygen in the water is reduced, and the growth of other organisms can also be influenced.
In the prior art, the treatment method of organic wastewater comprises biodegradation, adsorption, photocatalysis and the like. The related research of photodegradation of organic matters is more, and the organic matters are directly degraded into CO in the photodegradation process 2 And H 2 O and the like, is green and environment-friendly, does not need secondary treatment, and has wide research prospect.
The photocatalytic degradation technology needs the support of a photocatalytic material, and a common photocatalytic material is TiO 2 ZnO or correspondingly doped metal oxides, etc. The mechanism of photocatalysis is that ultraviolet light or visible light irradiates a photocatalysis material, and correspondingly generates holes (h) + ) And electrons (e) - ) And OH is reacted with - And O 2 Isooxidation-reduction to form OH and O 2 - The corresponding free radical. These radicals are highly reactive and readily reduce organic species to CO 2 And H 2 And (O). The photocatalysis can be carried out at room temperature, but the problems of long illumination time and low photocatalysis efficiency exist. MnO 2 Can also be used in the field of photocatalysis, but also has the problems of low photocatalysis efficiency and the like.
The common method for solving the problem of low catalytic efficiency of the photocatalyst is to carry out metal, nonmetal loading or other combination on the substrate catalystThe compound is modified by composite loading, or some cocatalyst such as H is added 2 O 2 、O 3 Persulfate (Na) 2 S 2 O 8 ) And the like are modified in cooperation with the photocatalyst. MnO 2 The photocatalyst has certain photocatalysis, but the photocatalyst has the problems of low photocatalysis efficiency and the like. Therefore, there is room for further research and development in the field of photocatalyst technology.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide an a-MnO-containing solution 2 The alpha-MnO with a nanowire morphology is prepared by the photocatalytic system 2 And with NaHSO 4 The composite system is formed cooperatively, has high photocatalytic efficiency, obvious degradation effect on various organic matters, high degradation efficiency and simple operation.
The technical scheme for realizing the aim of the invention is as follows:
alpha-MnO-containing 2 Comprising alpha-MnO 2 And NaHSO 4 (ii) a In the invention, a small amount of NaHSO is added 4 Namely, can be made to alpha-MnO 2 The photocatalytic efficiency of (a) plays a synergistic role, but the NaHSO is preferred 4 And alpha-MnO 2 The mass ratio of (A) to (B) is 0.05-1, and the synergistic effect is most obvious.
In the present invention, preferably, the α -MnO is 2 The crystal form is a specific crystal form and is prepared by the following preparation method: mixing KMnO 4 Dissolving in deionized water, and dripping MnSO under magnetic stirring 4 ·H 2 Obtaining mixed slurry in the water solution of O, transferring the mixed slurry into a stainless steel autoclave with a polytetrafluoroethylene lining, and preserving heat for 10-13h at the temperature of 130-145 ℃ in an oven; cooling the mixed slurry, carrying out suction filtration and washing, drying the obtained solid product in an oven, and calcining the dried solid product in a muffle furnace at 280-320 ℃ for 1.5-2.5h in the air atmosphere to obtain the alpha-MnO 2 It is in the shape of a nanowire.
In the present invention, preferably, the KMnO 4 The solid-liquid ratio of the deionized water to the deionized water is 1g; mnSO 4 ·H 2 O and KMnO 4 The molar ratio of (A) to (B) is 1.
In the invention, preferably, the drying temperature is 75-90 ℃, and the drying time is 10-14h.
The second purpose of the invention is to provide a material containing alpha-MnO 2 The preparation method of the photocatalytic system comprises the following steps:
(1) Preparation of alpha-MnO 2 : mixing KMnO 4 Dissolving in deionized water, and dripping MnSO under magnetic stirring 4 ·H 2 Obtaining mixed slurry in the water solution of O, transferring the mixed slurry into a stainless steel autoclave with a polytetrafluoroethylene lining, and preserving heat for 10-13h at the temperature of 130-145 ℃ in an oven; cooling the mixed slurry, performing suction filtration and washing, drying the obtained solid product in an oven, calcining the dried solid product in a muffle furnace at 280-320 ℃ in the air atmosphere for 1.5-2.5h to obtain the alpha-MnO 2 ；
(2) Will alpha-MnO 2 And NaHSO 4 And (5) subpackaging respectively. When in use, the components are respectively added.
The invention also aims to provide a new product containing alpha-MnO 2 The application of the photocatalytic system is to use the photocatalytic system in the degradation of organic polluted wastewater.
The specific application method comprises the following steps: adding a certain amount of alpha-MnO into organic polluted wastewater 2 Simultaneously adding a certain amount of NaHSO 4 And applying illumination to the organic matter polluted wastewater for more than 0.5h to obtain an obvious degradation effect.
Preferably, the α -MnO is optimized for optimal photocatalytic effect 2 The concentration of the waste water is 0.5g/L-3g/L.
The photocatalytic system of the invention has weak dependence on light sources, but has better effect of applying light with wavelength within the range of 200nm-800nm.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that: alpha-MnO of specific crystal form is used in the invention 2 With NaHSO 4 A strong oxidation-reduction system is constructed, and the degradation effect on various organic matters is obvious. Compared with the traditional Fenton-like photocatalysis technology and the like, the method has the advantages of low treatment cost, mild reaction system, no obvious secondary pollution and high cyclic utilization rate. The invention is toThe industrial organic polluted wastewater has very wide commercial application value.
Drawings
FIG. 1 shows alpha-MnO prepared in example 2 (scheme a) 2 X-ray diffraction patterns of (a);
FIG. 2 shows alpha-MnO prepared in example 2 (scheme a) 2 Scanning electron microscope images of;
FIG. 3 is a graph of the photocatalytic degradation rate of the photocatalytic system prepared in example 2 (scheme a) as a function of time;
FIG. 4 shows alpha-MnO prepared according to scheme b 2 X-ray diffraction patterns of (a);
FIG. 5 shows alpha-MnO prepared according to scheme b 2 Scanning electron microscope images of;
FIG. 6 is a graph showing the photocatalytic degradation rate of the photocatalytic system prepared in the scheme b as a function of time;
FIG. 7 shows alpha-MnO prepared in scheme c 2 X-ray diffraction pattern of
FIG. 8 shows alpha-MnO prepared according to scheme c 2 Scanning electron microscope image of
FIG. 9 shows alpha-MnO prepared in scheme c 2 A graph of the photocatalytic degradation rate of the photocatalytic system changing with time;
FIG. 10 shows α -MnO 2 The photocatalytic degradation ability of the synergy with different inorganic salts is compared.
Detailed Description
In order that the invention may be more clearly expressed, the invention is further illustrated by the following specific examples.
1. Preparation examples
Example 1
alpha-MnO-containing 2 Comprising alpha-MnO 2 And NaHSO 4 (ii) a And NaHSO 4 And alpha-MnO 2 The mass ratio of (1) is 0.05.
alpha-MnO-containing 2 Preparation of the photocatalytic system of (a): (1) 1gKMnO 4 Dissolving in 20ml deionized water, and adding dropwise MnSO 0.53g under magnetic stirring 4 ·H 2 15ml of water solution of O to obtain mixed slurry, and transferring the mixed slurry to a rotary kilnTransferring the mixture into a stainless steel autoclave with a polytetrafluoroethylene lining, and preserving heat for 13 hours in an oven at 130 ℃; cooling the mixed slurry, performing suction filtration and washing, drying the obtained solid product in a 75 ℃ oven for 14h, and calcining the dried solid product in a muffle furnace at 280 ℃ in the air atmosphere for 2.5h to obtain the alpha-MnO 2 It is in the shape of a nanowire.
(2) Will alpha-MnO 2 And NaHSO 4 Subpackaging respectively, and adding respectively when in use.
alpha-MnO-containing 2 The application of the photocatalytic system refers to that the photocatalytic system is used for degrading organic polluted wastewater. The specific method comprises the following steps: adding a certain amount of alpha-MnO into organic pollution wastewater 2 Using alpha-MnO 2 When the concentration of the wastewater is 0.5g/L, a certain amount of NaHSO is added simultaneously 4 So that NaHSO 4 And alpha-MnO 2 The mass ratio of the organic matter polluted wastewater is 0.05 to 1, the organic matter polluted wastewater is irradiated by light with the wavelength ranging from 200nm to 800nm for more than 0.5h, and then the obvious degradation effect can be seen.
Example 2
alpha-MnO-containing 2 Comprising alpha-MnO 2 And NaHSO 4 (ii) a And NaHSO 4 And alpha-MnO 2 The mass ratio of (1) is 0.8.
alpha-MnO-containing 2 Preparation of the photocatalytic system of (a): (1) 1.0g of KMnO 4 Dissolving in 25ml deionized water, and dripping into a solution containing 0.4g MnSO under magnetic stirring 4 ·H 2 O in 18ml of water solution to obtain mixed slurry, transferring the mixed slurry into a stainless steel autoclave with a polytetrafluoroethylene lining, and preserving heat for 12 hours in an oven at 140 ℃; cooling the mixed slurry, carrying out suction filtration and washing, drying the obtained solid product in an oven at 80 ℃ for 12h, and calcining the dried solid product in a muffle furnace at 300 ℃ in the air atmosphere for 2h to obtain the alpha-MnO 2 It is in the shape of a nanowire.
(2) Will alpha-MnO 2 And NaHSO 4 Subpackaging respectively, and adding respectively when in use.
alpha-MnO-containing 2 The application of the photocatalytic system refers to the application of the photocatalytic system in the degradation of organic polluted wastewater. The specific method comprises the following steps: direction machineAdding a certain amount of alpha-MnO into polluted wastewater 2 Let alpha-MnO 2 When the concentration of the wastewater is 1.25g/L, a certain amount of NaHSO is added at the same time 4 So that NaHSO 4 And alpha-MnO 2 The mass ratio of the organic matter polluted wastewater is 0.8, the organic matter polluted wastewater is irradiated by light with the wavelength ranging from 200nm to 800nm for more than 0.5h, and then the obvious degradation effect can be seen.
Example 3
alpha-MnO-containing 2 Comprising alpha-MnO 2 And NaHSO 4 (ii) a And NaHSO 4 And alpha-MnO 2 The mass ratio of (1).
alpha-MnO-containing 2 Preparation of the photocatalytic system of (a): (1) 1.0g of KMnO 4 Dissolving in 30ml deionized water, and dripping into a solution containing 0.3g MnSO under magnetic stirring 4 ·H 2 O in 20ml of water solution to obtain mixed slurry, transferring the mixed slurry into a stainless steel autoclave with a polytetrafluoroethylene lining, and preserving heat for 10 hours at 145 ℃ in an oven; cooling the mixed slurry, carrying out suction filtration and washing, drying the obtained solid product in an oven at 90 ℃ for 10h, calcining the solid product in a muffle furnace at 320 ℃ in an air atmosphere for 1.5h to obtain the alpha-MnO 2 It is in the shape of a nanowire.
(2) Will alpha-MnO 2 And NaHSO 4 Subpackaging respectively, and adding respectively when in use.
alpha-MnO-containing 2 The application of the photocatalytic system refers to the application of the photocatalytic system in the degradation of organic polluted wastewater. The specific method comprises the following steps: adding a certain amount of alpha-MnO into organic pollution wastewater 2 Using alpha-MnO 2 When the concentration of the wastewater is 0.5g/L-3g/L, a certain amount of NaHSO is added at the same time 4 So that NaHSO 4 And alpha-MnO 2 The mass ratio of the organic matter polluted wastewater is 1.
Analysis of the x-ray diffraction pattern of the product obtained in examples 1 to 3 revealed that the product was alpha-MnO 2 Wherein the x-ray diffraction pattern of example 2 is shown in figure 1; the microscopic morphology of the scanning electron microscope shows that the prepared MnO is 2 Is in the shape of a nanowire, in whichThe SEM image of example 2 is shown in FIG. 2.
2. Photocatalytic degradation test:
in order to better express the advantages of the present application, some research experiments on photocatalytic degradation are described as follows.
1. The photocatalytic degradation method comprises the following steps:
the application experiment of the product prepared by the example for catalytically degrading organic matters by taking methyl orange, rhodamine B and tetracycline hydrochloride organic matters as examples is described as follows: adding a photocatalyst into 40mL of methyl orange solution, rhodamine B solution and tetracycline hydrochloride solution with the concentration of 35mg/L respectively, standing in the dark for 30min to achieve adsorption/desorption balance, starting visible light irradiation, moving 2mL of solution from the solution every 20min, adding 1mL of methanol solution, performing suction filtration by using a filter head, filtering out solid particles, filling the filtrate into a cuvette, measuring the solution absorbance under the characteristic wavelength of organic matters (methyl orange: 464nm, rhodamine B: 554nm, tetracycline hydrochloride: 358 nm) respectively, and comparing the solution absorbance with the initial solution absorbance.
The photodegradation ratio (D) was calculated according to the following formula: d = (C) 0 -C t )/C 0 *100％＝(A 0 －A t )/A 0 *100% of, wherein C 0 Is the initial concentration of the solution, C t The concentration of the solution after the illumination time is t; c 0 Initial absorbance of the solution, C t The absorbance of the solution after the illumination time is t.
2. alpha-MnO of different crystal forms 2 Test of catalytic Effect of photocatalyst System
Scheme a: test group a photocatalytic test was performed using the photocatalytic system prepared in example 2, and the amount of the catalyst system added was the same as in example 2; comparative group a prepared by example 2 2 Performing a photocatalytic test, alpha-MnO 2 The addition amount of alpha-MnO of test group a 2 The addition amount of (A) is the same; the results of the photocatalytic degradation capability test for three organic compounds are shown in fig. 3.
Scheme b: test group b used the following recipePreparation of alpha-MnO 2 (ii) a By using NaHSO 4 And alpha-MnO 2 Adding the materials according to the mass ratio of 0.8 to 1, wherein the adding amount is the same as that of the catalyst system in the example 2, and performing a photocatalytic test as a photocatalytic system; alpha-MnO obtained by using test group b as comparison group b 2 Performing photocatalytic test, alpha-MnO 2 The addition amount of (c) and alpha-MnO in test group b 2 The addition amount of (A) is the same; the results of the photocatalytic degradation capability test on the three organic matters are shown in fig. 6;
alpha-MnO in test group b 2 The preparation method comprises the following steps: adding 8mmol K 2 S 2 O 8 、8mmolMnSO 4 ·H 2 O and 8mmolK 2 SO 4 Dissolving in 60mL of deionized water, adding 98wt% of 2 SO 4 The solution was 2mL. The solution was then transferred to a teflon lined stainless steel autoclave and heated in an oven at 140 ℃ for 12 hours. Finally, the a-MnO was collected by centrifugation 2 And (3) precipitating the nano particles, and drying at 105 ℃. The analysis result of the x-ray diffraction pattern of the obtained product indicates that the product is alpha type MnO 2 As shown in fig. 4. The microscopic morphology of the scanning electron microscope shows that the prepared MnO is 2 Is needle-shaped and gathered into dandelion flower shape, as shown in fig. 5.
Test group c: test group c prepared alpha-MnO by the following method 2 (ii) a By using NaHSO 4 And alpha-MnO 2 The catalyst is added according to the mass ratio of 0.8 to 1, the adding amount is the same as that of the catalyst system in the example 2, and the catalyst is used as a photocatalytic system to carry out a photocatalytic test; the comparison group c adopts alpha-MnO obtained by the test group c 2 Performing photocatalytic test, alpha-MnO 2 The addition amount of alpha-MnO in test group c 2 The addition amount of (A) is the same; the results of the photocatalytic degradation capability test on the three organic matters are shown in FIG. 9.
alpha-MnO in test group c 2 The preparation method comprises the following steps: adding 1.35g of potassium permanganate and 3.0ml of hydrochloric acid (37%) into 120ml of deionized water, dissolving the potassium permanganate and the hydrochloric acid, magnetically stirring the mixture for 30min, transferring the mixture into a high-pressure reaction kettle, putting the reaction kettle into a drying box, heating the mixture to 160 ℃, and reacting the mixture for 12 hours; naturally cooling to room temperature, filtering the obtained suspension, washing until the pH value is not changed, and drying the obtained sample in a drying oven at 80 ℃ for 24h to obtain the final product. The analysis result of the x-ray diffraction pattern of the obtained product shows that the product is alpha type MnO 2 As shown in fig. 7. The microscopic morphology of the scanning electron microscope shows that the prepared MnO is 2 It is needle-shaped and gathered into chestnut shell shape, as shown in FIG. 8.
As can be seen from the results of the photocatalytic degradation capability tests in fig. 3, 6, and 9, the a type MnO prepared by the three schemes 2 Alpha type MnO prepared by three schemes and having certain catalytic degradation capability 2 In synergy of NaHSO 4 Then, the photocatalytic degradation rate is obviously increased. Description of NaHSO 4 The addition of (2) is beneficial to the improvement of the photocatalytic efficiency. And the alpha type MnO prepared by the scheme a (the best scheme of the invention) 2 In synergy of NaHSO 4 Then, the degradation rates of methyl orange solution, rhodamine B solution and tetracycline hydrochloride solution are highest, and alpha type MnO prepared by schemes B and c is obtained 2 In synergy of NaHSO 4 Then, the degradation rate of the solution of methyl orange is higher, but the improvement effect of the degradation rate of the solution of rhodamine B and the tetracycline hydrochloride solution is obviously inferior to that of the scheme a; description of preparation of scheme a 2 In synergy of NaHSO 4 The photocatalytic effect is then optimal.
3. Test of Effect of ions on photocatalytic Properties
alpha-MnO prepared as in example 2 2 The catalyst is a main catalyst body, the adding amount of the catalyst is 0.05 g in a unified mode, the adding amount of other inorganic salts is 0.04g in a unified mode, and the using amount of methyl orange is 40mL, and the concentration is 35mg/L. Other inorganic salts are discussed, including Na 2 SO 4 、 NaHSO 3 、NaHSO 4 、MnSO 4 、NaNO 3 、NaH 2 PO 4 And alpha-MnO 2 The result of the synergistic effect on the photocatalytic degradation of methyl orange is shown in fig. 10. It can be seen that the alpha-MnO prepared by the present invention 2 With NaHSO 4 After the synergistic effect, the photocatalytic degradation rate is far higher than that of other groups, and the photocatalytic effect is optimal.
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.
Claims (7)
1. alpha-MnO-containing 2 Characterized in that: comprising alpha-MnO 2 And NaHSO 4 Said NaHSO 4 And alpha-MnO 2 The mass ratio of (A) to (B) is 0.05-1; the alpha-MnO 2 The crystal form is a specific crystal form and is prepared by the following preparation method: mixing KMnO 4 Dissolving in deionized water, and adding dropwise MnSO under magnetic stirring 4 ·H 2 Obtaining mixed slurry in the water solution of O, transferring the mixed slurry into a stainless steel autoclave with a polytetrafluoroethylene lining, and preserving heat for 10-13h at the temperature of 130-145 ℃ in an oven; cooling the mixed slurry, carrying out suction filtration and washing, drying the obtained solid product in an oven, and calcining the dried solid product in a muffle furnace at 280-320 ℃ for 1.5-2.5h in the air atmosphere to obtain the alpha-MnO 2 (ii) a The photocatalytic system is used for degrading organic polluted wastewater containing methyl orange, tetracycline and rhodamine B.
2. The alpha-MnO-containing system of claim 1, wherein the alpha-MnO is a solution of 2 Characterized in that: the KMnO 4 The solid-liquid ratio of the deionized water to the deionized water is 1g; mnSO 4 ·H 2 O and KMnO 4 The molar ratio of (A) to (B) is 1.
3. The alpha-MnO-containing system of claim 1 2 Characterized in that: the drying temperature is 75-90 ℃, and the drying time is 10-14h.
4. The alpha-MnO-containing product according to any one of claims 1 to 3, wherein the alpha-MnO is a product containing alpha-MnO 2 The method for producing a photocatalytic system according to (1), characterized by comprising the steps of:
(1) Preparation of alpha-MnO 2 : mixing KMnO 4 Dissolving in deionized water, and dripping MnSO under magnetic stirring 4 ·H 2 O in water to obtain mixed slurry, transferring the mixed slurry into a stainless steel autoclave with a polytetrafluoroethylene lining, andkeeping the temperature in an oven at 130-145 ℃ for 10-13h; cooling the mixed slurry, performing suction filtration and washing, drying the obtained solid product in an oven, and calcining the dried solid product in a muffle furnace at 280-320 ℃ for 1.5-2.5h in an air atmosphere to obtain the alpha-MnO 2 ；
(2) Will alpha-MnO 2 And NaHSO 4 And (5) subpackaging respectively.
5. The alpha-MnO-containing system of claim 1 2 The use of a photocatalytic system according to (1), characterized in that: the specific application method comprises the step of adding a certain amount of alpha-MnO into the organic polluted wastewater 2 Simultaneously adding a certain amount of NaHSO 4 And applying illumination to the organic matter polluted wastewater for more than 0.5h to obtain an obvious degradation effect.
6. The alpha-MnO-containing system of claim 5 2 The use of a photocatalytic system according to (1), characterized in that: the alpha-MnO 2 The concentration of the waste water is 0.5g/L-3g/L.
7. The alpha-MnO-containing system of claim 5 2 The use of a photocatalytic system according to (1), characterized in that: the light wavelength range of the illumination is 200nm-800nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011527438.7A CN112588302B (en) | 2020-12-22 | 2020-12-22 | alpha-MnO-containing 2 Photocatalytic system, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011527438.7A CN112588302B (en) | 2020-12-22 | 2020-12-22 | alpha-MnO-containing 2 Photocatalytic system, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112588302A CN112588302A (en) | 2021-04-02 |
| CN112588302B true CN112588302B (en) | 2022-12-13 |
Family
ID=75199888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011527438.7A Active CN112588302B (en) | 2020-12-22 | 2020-12-22 | alpha-MnO-containing 2 Photocatalytic system, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112588302B (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3871881A (en) * | 1973-02-12 | 1975-03-18 | Minnesota Mining & Mfg | Coated aluminum substrates having a binder of aluminum hydroxyoxide |
| HK1069716A2 (en) * | 2004-03-31 | 2005-05-27 | Acumen Environmental Engineeri | Enhanced photocatalytic system. |
| CN101950682B (en) * | 2010-09-09 | 2012-09-19 | 江西财经大学 | Preparation method of super-capacitor manganese oxide material |
| CN104693844A (en) * | 2013-12-07 | 2015-06-10 | 青岛水世界环保科技有限公司 | Environment-friendly photocatalyzed nano composite coating |
| CN104628039B (en) * | 2015-02-06 | 2016-04-27 | 南京工业大学 | A kind of controllable method for preparing of α-manganese dioxide nanowire |
| CN106111082B (en) * | 2016-04-25 | 2019-01-29 | 河池学院 | The CO of high activity2Adsorbent and preparation method thereof |
| CN106732542A (en) * | 2016-12-09 | 2017-05-31 | 福州大学 | One-step method prepares sheet manganese dioxide/carbon fibers at low temperature denitrating catalyst |
| CN108212192A (en) * | 2018-01-19 | 2018-06-29 | 西安工业大学 | A kind of light-fenton catalyst and preparation method thereof |
-
2020
- 2020-12-22 CN CN202011527438.7A patent/CN112588302B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112588302A (en) | 2021-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108273492B (en) | Bismuth oxide/bismuth tetroxide heterojunction photocatalyst and preparation method and application thereof | |
| CN106732524B (en) | Alpha/beta-bismuth oxide phase heterojunction photocatalyst and preparation method and application thereof | |
| CN111604077B (en) | g-C for degrading ammonia nitrogen3N4/Gr/TiO2Z-system photocatalytic material and preparation method and application thereof | |
| CN106824213B (en) | Cobalt oxide doped bismuth subcarbonate/bismuth oxychloride photocatalyst and preparation method thereof | |
| CN107555481B (en) | Manganese oxide material and preparation method thereof | |
| CN104722302A (en) | Acidified mixed crystal TiO2 nanowire loaded photocatalyst and preparation and application of photocatalyst | |
| CN107442100B (en) | Preparation method and application of porous hollow-structure gallium sesquioxide photocatalyst | |
| CN113559858B (en) | Preparation method and application of biochar-based composite material | |
| CN109250755A (en) | A kind of bismuth oxide photocatalyst and preparation method thereof of the different crystal phases containing bismuth defect | |
| CN112076741B (en) | CeO (CeO) 2 /Bi 2 O 4 Composite visible light catalyst and preparation method thereof | |
| Pei et al. | A one-pot hydrothermal synthesis of Eu/BiVO4 enhanced visible-light-driven photocatalyst for degradation of tetracycline | |
| CN114570348B (en) | Titanium dioxide-based nano composite photocatalyst for photocatalytic degradation by irradiation of visible light and application thereof | |
| CN112403467A (en) | TiO2Co-doped composite photocatalyst, preparation method thereof and application thereof in treating phenol-containing wastewater | |
| CN110090657B (en) | Sepiolite composite catalyst, preparation method thereof, novel Fenton-like system and application thereof | |
| CN105561969B (en) | A kind of porous TixSn1-xO2The preparation and application of solid solution microballoon | |
| CN112588302B (en) | alpha-MnO-containing 2 Photocatalytic system, preparation method and application thereof | |
| CN111545211A (en) | Graphene oxide-lanthanum oxide-cobalt hydroxide composite material, and synthesis method and application thereof | |
| CN114433107B (en) | Co (cobalt) 3 O 4 /Bi 4 O 7 /Bi 2 O 3 Heterojunction photocatalyst and application thereof | |
| CN113019374B (en) | NiO/ZrO 2 Preparation method of nano composite photocatalyst and application of catalyst | |
| CN110776079A (en) | Method for promoting phenol pollutants to be efficiently photo-catalytically oxidized in situ by utilizing organic arsenic pollutants | |
| CN109201036B (en) | Preparation method of visible light photocatalyst for water treatment process | |
| CN112973671A (en) | Nano bismuth tungstate/zinc oxide heterojunction catalyst, preparation method and application thereof | |
| CN111905708A (en) | Preparation method and application of solid zinc oxide microspheres | |
| Jing et al. | β-FeOOH/TiO 2/cellulose nanocomposite aerogel as a novel heterogeneous photocatalyst for highly efficient photo-Fenton degradation | |
| CN117504892B (en) | La-Fe co-doped SrTiO3/TiO2Composite material, 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 |