CN114950517B - Photocatalyst for efficiently degrading organic pollutants as well as preparation method and application thereof - Google Patents
Photocatalyst for efficiently degrading organic pollutants as well as preparation method and application thereof Download PDFInfo
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- CN114950517B CN114950517B CN202110213535.7A CN202110213535A CN114950517B CN 114950517 B CN114950517 B CN 114950517B CN 202110213535 A CN202110213535 A CN 202110213535A CN 114950517 B CN114950517 B CN 114950517B
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 46
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 39
- 230000000593 degrading effect Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- CBACFHTXHGHTMH-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-phenyl-2-piperidin-1-ylacetate;dihydrochloride Chemical compound Cl.Cl.C1CCCCN1C(C=1C=CC=CC=1)C(=O)OCCN1CCCCC1 CBACFHTXHGHTMH-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 14
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- 230000015556 catabolic process Effects 0.000 claims description 11
- 238000006731 degradation reaction Methods 0.000 claims description 11
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims description 8
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 8
- 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 8
- 229940012189 methyl orange Drugs 0.000 claims description 8
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229940090668 parachlorophenol Drugs 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 6
- -1 nitrogen-containing compound Chemical class 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000001338 self-assembly Methods 0.000 claims description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 2
- 229960003742 phenol Drugs 0.000 claims description 2
- 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 2
- 229940043267 rhodamine b Drugs 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 14
- 229910002804 graphite Inorganic materials 0.000 abstract description 14
- 239000010439 graphite Substances 0.000 abstract description 14
- 238000009826 distribution Methods 0.000 abstract description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 230000006798 recombination Effects 0.000 abstract description 4
- 238000005215 recombination Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 26
- 239000000243 solution Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 238000001035 drying Methods 0.000 description 11
- 238000001914 filtration Methods 0.000 description 9
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- 238000004519 manufacturing process Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 229910000416 bismuth oxide Inorganic materials 0.000 description 5
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004098 Tetracycline Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229960002180 tetracycline Drugs 0.000 description 2
- 229930101283 tetracycline Natural products 0.000 description 2
- 235000019364 tetracycline Nutrition 0.000 description 2
- 150000003522 tetracyclines Chemical class 0.000 description 2
- WUPZAQSKRMYJNB-MDZDMXLPSA-N 1,1'-azobis-1,2,3-triazole Chemical compound N1=NC=CN1\N=N\N1N=NC=C1 WUPZAQSKRMYJNB-MDZDMXLPSA-N 0.000 description 1
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- FTLHORLYDROOSU-UHFFFAOYSA-N indium(3+);trinitrate;pentahydrate Chemical compound O.O.O.O.O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FTLHORLYDROOSU-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
-
- 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
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- 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
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- 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 belongs to the field of environmental catalysis, and discloses a photocatalyst for efficiently degrading organic pollutants under visible light, and a preparation method and application thereof. The preparation method comprises the steps of preparing bismuth oxyiodide through water dispersion, constructing a supermolecular network through a nitrogen-rich compound, enabling the bismuth oxyiodide to be uniformly distributed in the supermolecular network as much as possible through constant temperature reaction, and finally enabling the photocatalyst to be molded through high-temperature roasting. Compared with the preparation of graphite phase carbon nitride and reconstruction of heterojunction materials, the photocatalyst provided by the invention has the advantages that the graphite phase carbon nitride has special globular shape instead of the traditional block shape or two-dimensional lamellar shape, and more ideal surface distribution can effectively inhibit the recombination of photo-generated electrons and holes, so that more photo-generated electrons can reach the surface of the catalyst to combine with oxygen molecules to form superoxide radicals, and better photocatalytic degradation capacity (38% improvement compared with the conventional photocatalyst) is achieved.
Description
Technical Field
The invention belongs to the field of environmental catalysis, and in particular relates to a photocatalyst for efficiently degrading organic pollutants under visible light, and a preparation method and application thereof.
Background
The environmental pollution problem is a serious problem facing the 21 st century human beings, and in the process of resisting the environmental pollution, a plurality of technical means are active and burst, and the environmental catalysis technology is one of the important technical means. The visible light photocatalysis technology is one of the key research directions in the current catalysis field, has the advantages of the common catalysis technology such as mild reaction conditions, and has other special advantages such as providing energy required by the reaction by using the visible light with lower energy in sunlight (natural light), reducing energy consumption and saving cost. When the visible light photocatalysis technology is adopted to treat organic matters in environmental pollutants, the catalyst is irradiated by visible light to excite photo-generated electrons with reducing capability and holes with oxidizing capability, and the organic pollutants can be oxidized or mineralized and degraded into small molecules or carbon dioxide and water through a certain oxidation-reduction reaction in a reaction system, so that the removal of the organic pollutants is realized, and the aim of environmental purification is fulfilled.
Most of organic pollutants are due to improper treatment or difficult treatment of organic compounds in the production process, and after being discharged into the environment, the organic pollutants are naturally degraded slowly due to higher physical and chemical stability, so that the ecological system is influenced to a certain extent, and even the balance of the local ecological system can be destroyed. These compounds are important raw materials or products of social production and become pollutants when improperly handled into the natural environment. The problem of degrading the organic pollutants becomes a scientific research and social environment problem with great practical value due to the two sides of the organic pollutants to economy and environment. In Chinese patent publication CN111437856A, a heterojunction catalyst with excellent performance is prepared by firstly preparing graphite phase carbon nitride nanotubes and then growing bismuth oxyhalide on the graphite phase carbon nitride nanotubes through hydrothermal reaction, so that the degradation rate of tetracycline under visible light is greatly improved. However, concentrated sulfuric acid is required in the preparation process, so that the operation requirement on the production process is increased, and the production risk is also increased; in addition, solvents such as methanol and ethylene glycol are used for many times in the preparation process, so that the control of the production cost is unfavorable, and the method is not favorable for large-scale popularization and use. In chinese patent publication CN111097477a, a graphite-phase carbon nitride nano-sheet is obtained by roasting urea twice, then a composite of the graphite-phase carbon nitride nano-sheet and graphene oxide is obtained by mixing and refluxing, and finally the composite is mixed and refluxed in a mixed solution of indium nitrate pentahydrate, cetyltrimethylammonium bromide and thioacetamide, thereby obtaining an ultrathin two-dimensional layered composite photocatalytic material, and having a large effect on removal of tetracycline. However, the lack of high temperature sintering may result in poor bonding between the catalyst components and poor mechanical strength.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the primary purpose of the invention is to provide a preparation method of a photocatalyst for efficiently degrading organic pollutants under visible light.
The invention also aims to provide the photocatalyst for efficiently degrading organic pollutants under the visible light, which is prepared by the method.
The invention also aims to provide the application of the photocatalyst for efficiently degrading organic pollutants under the visible light in the catalytic degradation of the organic pollutants.
The aim of the invention is achieved by the following scheme:
the preparation process of the photocatalyst for efficiently degrading organic pollutants under visible light comprises three parts, namely, firstly preparing bismuth oxyiodide precursor and nitrogen-containing organic matter supermolecule, then fully mixing the bismuth oxyiodide precursor and the nitrogen-containing organic matter supermolecule, and then filtering, drying and roasting to obtain the catalyst.
The method specifically comprises the following steps:
(1) Bismuth oxyiodide is prepared by reacting bismuth nitrate pentahydrate and potassium iodide in water;
(2) Heating the nitrogen-containing compound in water to self-assemble to obtain a supermolecular compound;
(3) Mixing bismuth oxyiodide prepared in the step (1) with the supermolecular compound prepared in the step (2) for reaction to obtain a photocatalyst precursor;
(4) And (3) putting the obtained precursor into a ceramic crucible paved with aluminum foil, coating the aluminum foil outside the crucible to form a closed space, heating and roasting in a muffle furnace, and naturally cooling to obtain the photocatalyst.
The molar ratio of the bismuth nitrate pentahydrate to the potassium iodide in the step (1) is 1:0.1-10; preferably 1:1.
The reaction in the step (1) is stirring reaction for 30-480min at room temperature; preferably 240min.
In the step (1), for more sufficient reaction, bismuth nitrate pentahydrate and potassium iodide are preferably dissolved in water to form an aqueous solution, and then mixed for reaction.
The nitrogen-containing compound in the step (2) is at least one of melamine, 5-aminotetrazole, azotriazole and cyanuric acid; preferably melamine and cyanuric acid; more preferably the molar ratio is 1:1 melamine and cyanuric acid.
The heating self-assembly in the step (2) means heating to 60-120 ℃ for reaction for 30-360min.
In step (2), for more sufficient reaction, it is preferable to dissolve the nitrogen-containing compound in water separately, mix them, and heat the mixture to self-assemble.
The mass ratio of the bismuth oxyiodide to the supermolecular compound in the step (3) is 1:0.1-10; preferably 1:4, a step of;
the mixing reaction in the step (3) is carried out in an aqueous solution at 60-120 ℃ for 30-360min.
And (3) after the mixing reaction is finished, further comprising post-treatment operations such as filtering, washing, drying, grinding and the like.
The heating and roasting in the step (4) means that the temperature is raised to 350-650 ℃ at 1-10 ℃ and the reaction is carried out for 30-360min. Preferably, the temperature is raised to 500 ℃ at a heating rate of 10 ℃/min and the mixture is baked for 2 hours at constant temperature.
The photocatalyst for efficiently degrading organic pollutants under visible light, which is prepared by the method, consists of high-dispersity small spherical graphite phase carbon nitride and Gao Wendian bismuth oxide resistant, wherein Gao Wendian bismuth oxide resistant is prepared by high-temperature roasting after bismuth oxyiodide acts on the supermolecular compound; the graphite phase carbon nitride is in a small sphere shape and is highly dispersed on the surface of the Gao Wendian bismuth oxide resistant material; the Gao Wendian bismuth oxide is three-dimensional rose-like and has fewer lamellar units of bismuth oxyiodide than typical bismuth oxyiodide.
The photocatalyst for efficiently degrading organic pollutants under visible light is applied to catalytic degradation of organic pollutants.
The organic pollutant is one of tetracycline hydrochloride, methyl orange, phenol, parachlorophenol, rhodamine B, methylene blue and the like; preferably one of tetracycline hydrochloride, methyl orange, and p-chlorophenol.
The mechanism of the invention is as follows:
the preparation method comprises the steps of preparing bismuth oxyiodide through water dispersion, constructing a supermolecular network through a nitrogen-rich compound, enabling the bismuth oxyiodide to be uniformly distributed in the supermolecular network as much as possible through constant temperature reaction, and finally enabling the photocatalyst to be molded through high-temperature roasting. On one hand, the dispersing medium used in the preparation process is water, and no other solvent is used, so that the technical requirements on reaction equipment can be greatly reduced, and the raw material cost and the separation cost in the production process can be saved. On the other hand, the preparation process only needs to perform one-time high-temperature roasting, so that the graphite phase carbon nitride and bismuth oxyiodide are tightly combined while the energy consumption is saved, the interface electron conduction resistance is reduced, and the photocatalytic activity is improved. Because the supermolecular compound generates ammonia gas and carbon dioxide gas in the constant-temperature roasting process, the formed graphite-phase carbon nitride is highly dispersed in Gao Wendian bismuth oxide, and meanwhile, the morphological characteristics of the formed graphite-phase carbon nitride tend to be small spheres due to the space limitation of the three-dimensional rose-shaped bismuth oxyiodide; for bismuth oxyiodide, the ammonia gas and the carbon dioxide gas have gas stripping action, so that the high-temperature resistant bismuth oxyiodide is formed, the appearance of the high-temperature resistant bismuth oxyiodide is approximately consistent with that of the conventional bismuth oxyiodide, the high-temperature resistant bismuth oxyiodide is in a three-dimensional rose shape, and the high-temperature resistant bismuth oxyiodide has fewer lamellar unit bismuth oxyiodide compared with the typical bismuth oxyiodide.
Compared with the prior art, the invention has the following advantages:
compared with the preparation of graphite phase carbon nitride and reconstruction of heterojunction material (comparative example 3), the photocatalyst provided by the invention has the advantages that the graphite phase carbon nitride has a special small sphere (figure 2) instead of the traditional block or two-dimensional lamellar (figure 4), and more ideal surface distribution can more effectively inhibit the recombination of photo-generated electrons and holes, so that more photo-generated electrons can reach the surface of the catalyst to combine with oxygen molecules to form superoxide radicals, thereby bringing about better photocatalytic degradation capability (38% improvement compared with the prior art).
The photocatalyst with high dispersity prepared by the invention can realize the purpose of efficiently degrading organic pollutants under the condition of visible light, and has certain reference value and practicability for removing the organic pollutants in wastewater treatment. The invention has the advantages of easily obtained raw materials, low price, simple and convenient method, environmental protection and suitability for large-scale popularization and use.
Drawings
Fig. 1 is an SEM morphology diagram of the photocatalyst for efficiently degrading organic pollutants under visible light prepared in example 1.
Fig. 2 is a high resolution scanning electron microscope image of a photocatalyst for efficiently degrading organic pollutants under visible light prepared in example 1.
Fig. 3 is an elemental distribution diagram of a photocatalyst for efficiently degrading organic pollutants under visible light prepared in example 1.
FIG. 4 shows a photocatalyst g-C prepared in comparative example 3 3 N 4 Field emission scanning electron microscope image of/BiOI.
FIG. 5 is a graph showing the comparative activities of photocatalytic degradation of tetracycline hydrochloride in example 1 and comparative example 2.
FIG. 6 is a comparative graph of photocatalytic degradation methyl orange activity for example 1 and comparative examples 1, 2, and 3.
FIG. 7 is a graph showing the comparison of activities of photocatalytic degradation of parachlorophenol in example 1 and comparative example 2.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available as usual unless otherwise specified.
Example 1: preparation method of photocatalyst for efficiently degrading organic pollutants under visible light
A preparation method of a photocatalyst for efficiently degrading organic pollutants under visible light comprises the following steps:
(1) At room temperature, respectively weighing 2.425g of bismuth nitrate pentahydrate and 0.830g of potassium iodide, respectively dispersing in 130 ml of water and 20 ml of water, and uniformly stirring; dropwise (1 drop/second) adding the potassium iodide solution into the bismuth nitrate solution, and continuously stirring for 120 minutes; filtering, washing and drying to obtain bismuth oxyiodide.
(2) 1.261g of melamine and 1.291g of cyanuric acid are respectively weighed and respectively dispersed in 100ml of hot water at 90 ℃ and stirred for 30 minutes; dropwise adding the melamine solution into the cyanuric acid solution (1 drop/second) and continuously stirring for 30 minutes; adding 0.528g of bismuth oxyiodide obtained in the step (1), and stirring for 60 minutes; filtering, washing and drying to obtain the photocatalyst precursor.
(3) And (3) placing the precursor obtained in the step (2) into a ceramic crucible, covering a cover, placing into a muffle furnace, heating to 500 ℃ at a heating rate of 10 ℃/min under the air condition, roasting at constant temperature for 2 hours, and naturally cooling to obtain the photocatalyst for efficiently degrading organic pollutants under visible light.
The SEM morphology of the photocatalyst for efficiently degrading organic pollutants under visible light obtained in example 1 is shown in fig. 1, and it can be seen from fig. 1 that the catalyst body presents a three-dimensional structure, probably due to the stereo self-assembly of bismuth oxyiodide, while graphite-phase carbon nitride does not observe a significant layered stacking structure, so that we perform higher resolution morphology characterization to determine the morphology of the catalyst.
The high-resolution scanning electron microscope image of the photocatalyst for efficiently degrading organic pollutants under visible light obtained in example 1 is shown in fig. 2, and it can be seen from fig. 2 that graphite-phase carbon nitride presents special island-shaped distribution on the surface of bismuth oxyiodide, and the graphite-phase carbon nitride is not stacked in a traditional lamellar manner, so that the transmission path of carriers can be optimized, the recombination condition of photo-generated electron-hole pairs can be reduced, the service life of photo-generated electrons can be prolonged, and the photo-catalytic activity can be improved.
The element distribution diagram of the photocatalyst for efficiently degrading organic pollutants under visible light obtained in example 1 is shown in fig. 3, and it can be seen from fig. 3 that the distribution of elements such as C, N, O, I, bi can be observed in the element distribution on the surface of the catalyst, which indicates that the catalyst may contain graphite-phase carbon nitride and bismuth oxyiodide, and the graphite-phase carbon nitride presents relatively uniform dispersion on the surface of the bismuth oxyiodide, as seen in combination with fig. 1 and 2.
Comparative example 1: preparation method of graphite phase carbon nitride
A method for preparing graphite phase carbon nitride, comprising the following steps:
(1) 1.261g of melamine and 1.291g of cyanuric acid are respectively weighed and respectively dispersed in 100ml of hot water at 90 ℃ and stirred for 30 minutes; dropwise adding the melamine solution A into the cyanuric acid solution B (1 drop/second) and stirring for 30 minutes; filtering, washing and drying to obtain the precursor of the comparative example 1.
(2) Placing the precursor obtained in the step (1) into a ceramic crucible, covering a cover, placing into a muffle furnace, heating to 500 ℃ at a heating rate of 10 ℃/min under the air condition, roasting at constant temperature for 2 hours, and naturally cooling to obtain graphite-phase carbon nitride of the comparative example 1;
comparative example 2: preparation method of bismuth oxyiodide
A method for preparing bismuth oxyiodide of comparative example 2, comprising the steps of:
(1) At room temperature, respectively weighing 2.425g of bismuth nitrate pentahydrate and 0.830g of potassium iodide, respectively dispersing in 130 ml of water and 20 ml of water, and uniformly stirring; dropwise (1 drop/second) adding the potassium iodide solution into the bismuth nitrate solution, and continuously stirring for 120 minutes; filtering, washing and drying to obtain bismuth oxyiodide.
(2) 1.261g of bismuth oxyiodide and 1.291g of bismuth oxyiodide are respectively weighed and respectively dispersed in 100ml of hot water at 90 ℃ and stirred for 30 minutes; dropwise adding the bismuth oxyiodide solution A into the bismuth oxyiodide solution B (1 drop/second), and stirring for 30 minutes; 0.528g bismuth oxyiodide was added and stirring continued for 60 minutes; filtering, washing and drying to obtain the precursor of the comparative example 2.
(3) Placing the precursor obtained in the step (2) into a ceramic crucible, covering a cover, placing into a muffle furnace, heating to 500 ℃ at a heating rate of 10 ℃/min under the air condition, roasting at constant temperature for 2 hours, and naturally cooling to obtain the bismuth oxyiodide of the comparative example 2;
comparative example 3: photocatalyst g-C 3 N 4 Preparation method of BiOI
Photocatalyst g-C of comparative example 3 3 N 4 A process for preparing BiOI, which comprises the following stepsThe steps are as follows:
(1) At room temperature, respectively weighing 2.425g of bismuth nitrate pentahydrate and 0.830g of potassium iodide, respectively dispersing in 130 ml of water and 20 ml of water, and uniformly stirring; dropwise (1 drop/second) adding the potassium iodide solution into the bismuth nitrate solution, and continuously stirring for 120 minutes; filtering, washing and drying to obtain bismuth oxyiodide.
(2) 1.261g of melamine and 1.291g of cyanuric acid are respectively weighed and respectively dispersed in 100ml of hot water at 90 ℃ and stirred for 30 minutes; dropwise adding the melamine solution A into the cyanuric acid solution B (1 drop/second) and stirring for 90 minutes; filtering, washing and drying to obtain the precursor of graphite phase carbon nitride.
(3) Placing the precursor obtained in the step (2) into a ceramic crucible, covering a cover, placing into a muffle furnace, heating to 500 ℃ at a heating rate of 10 ℃/min under the air condition, roasting for 2 hours at constant temperature, and naturally cooling to obtain graphite-phase carbon nitride;
(4) Putting all graphite-phase carbon nitride obtained in the step (3) and 0.528g of bismuth oxyiodide obtained in the step (1) into a stainless steel reaction kettle with a perfluoroethylene lining, sealing, placing into a temperature programming drying oven at a constant temperature of 140 ℃ for 12 hours, cooling, carrying out suction filtration to obtain a product, and cleaning with deionized water and absolute ethyl alcohol for three times respectively; placing the washed product in a vacuum drying oven, drying at 80 ℃ for 12 hours to finally obtain the photocatalyst g-C of the comparative example 3 3 N 4 /BiOI。
Comparative example 3 photocatalyst g-C 3 N 4 A field emission scanning electron micrograph of/BiOI is shown in FIG. 4. Compared with the preparation of graphite phase carbon nitride and reconstruction of heterojunction material (comparative example 3), the photocatalyst provided by the invention has the advantages that the graphite phase carbon nitride has a special small sphere (figure 2) instead of the traditional block or two-dimensional lamellar (figure 4), and more ideal surface distribution can more effectively inhibit the recombination of photo-generated electrons and holes, so that more photo-generated electrons can reach the surface of the catalyst to combine with oxygen molecules to form superoxide radicals, thereby bringing about better photocatalytic degradation capability (38% improvement compared with the prior art).
The photocatalyst prepared in the example 1 of the invention is used for degrading tetracycline hydrochloride, the catalyst dosage is 30mg, the simulated wastewater of tetracycline hydrochloride (10 mg/L,100 mL) is continuously illuminated for 60 minutes, the degradation rate of tetracycline hydrochloride is 82.2%, and under the same condition, the degradation rate of tetracycline hydrochloride is 8.6% in the comparative example 1 and 64.8% in the comparative example 2. As shown in particular in fig. 5.
Under the same illumination condition, the photocatalyst prepared in the embodiment 1 of the invention continuously irradiates methyl orange, the catalyst dosage is 30mg, the simulated wastewater of the methyl orange (10 mg/L,100 mL) is continuously irradiated for 30 minutes, the degradation rate of the methyl orange is 99.4%, the degradation rate of the methyl orange is 18.8% in comparative example 1, 64.8% in comparative example 2 and g-C in comparative example 3 3 N 4 The degradation rate of/BiOI was 72.1%. As shown in particular in fig. 6.
Under the same illumination condition, the photocatalyst prepared in the example 1 of the invention is used for continuously illuminating parachlorophenol, the catalyst dosage is 30mg, the simulated wastewater of parachlorophenol (10 mg/L,100 mL) is continuously illuminated for 60 minutes, the degradation rate of parachlorophenol is 27.9%, and the degradation rate of parachlorophenol is 1.3% in the comparative example 1 and 16.3% in the comparative example 2. As particularly shown in fig. 7.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (7)
1. The preparation method of the photocatalyst for efficiently degrading organic pollutants under visible light is characterized by comprising the following steps of:
(1) Bismuth oxyiodide is prepared by reacting bismuth nitrate pentahydrate and potassium iodide in water;
(2) Heating the nitrogen-containing compound in water to self-assemble to obtain a supermolecular compound;
(3) Mixing bismuth oxyiodide prepared in the step (1) with the supermolecular compound prepared in the step (2) for reaction to obtain a photocatalyst precursor;
(4) Placing the obtained precursor into a ceramic crucible paved with aluminum foil, coating the aluminum foil outside the crucible to form a closed space, heating and roasting in a muffle furnace, and naturally cooling to obtain the photocatalyst;
the nitrogen-containing compound in the step (2) is melamine and cyanuric acid;
the heating self-assembly in the step (2) means heating to 60-120 ℃ for reaction for 30-360min;
the mass ratio of the bismuth oxyiodide to the supermolecular compound in the step (3) is 1:0.1-10;
the mixing reaction in the step (3) is carried out in an aqueous solution at 60-120 ℃ for 30-360min.
2. The method for preparing the photocatalyst for efficiently degrading organic pollutants under visible light according to claim 1, wherein the method comprises the following steps:
the molar ratio of the bismuth nitrate pentahydrate to the potassium iodide in the step (1) is 1:0.1-10;
the reaction in the step (1) is stirred at room temperature for 30-480min.
3. The method for preparing the photocatalyst for efficiently degrading organic pollutants under visible light according to claim 1, wherein the method comprises the following steps:
the molar ratio of the nitrogen-containing compound in the step (2) is 1:1 melamine and cyanuric acid.
4. The method for preparing the photocatalyst for efficiently degrading organic pollutants under visible light according to claim 1, wherein the method comprises the following steps:
the heating and roasting in the step (4) means heating to 350-650 ℃ at 1-10 ℃ per minute, and reacting for 30-360min at a constant temperature.
5. A photocatalyst for efficiently degrading organic pollutants under visible light, prepared by the method according to any one of claims 1 to 4.
6. The use of the photocatalyst for efficiently degrading organic pollutants under visible light according to claim 5 in catalytic degradation of organic pollutants.
7. The use of the photocatalyst for efficiently degrading organic pollutants under visible light according to claim 6, characterized in that:
the organic pollutant is one of tetracycline hydrochloride, methyl orange, phenol, parachlorophenol, rhodamine B and methylene blue.
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