CN114618591A - g-C3N4@ ZIF-8 composite photocatalyst and preparation method and application thereof - Google Patents
g-C3N4@ ZIF-8 composite photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 126
- 239000011259 mixed solution Substances 0.000 claims abstract description 83
- 239000000843 powder Substances 0.000 claims abstract description 55
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 239000004202 carbamide Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 17
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000004729 solvothermal method Methods 0.000 claims abstract description 15
- 238000001291 vacuum drying Methods 0.000 claims abstract description 13
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 31
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 29
- 239000002244 precipitate Substances 0.000 claims description 28
- 238000003760 magnetic stirring Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000003344 environmental pollutant Substances 0.000 claims description 4
- 231100000719 pollutant Toxicity 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical group Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 102100029880 Glycodelin Human genes 0.000 claims 1
- 101000585553 Homo sapiens Glycodelin Proteins 0.000 claims 1
- 230000000593 degrading effect Effects 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 238000005979 thermal decomposition reaction Methods 0.000 claims 1
- 239000013167 zeolitic imidazolate framework-1 Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004140 cleaning Methods 0.000 abstract description 5
- 238000005336 cracking Methods 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 2
- 238000006557 surface reaction Methods 0.000 abstract description 2
- 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 description 20
- 229960000907 methylthioninium chloride Drugs 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- -1 printing and dyeing Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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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
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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
- 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
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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
- 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
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- 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
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- 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
- C02F2305/08—Nanoparticles or nanotubes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2305/10—Photocatalysts
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Abstract
The invention provides a g-C3N4The @ ZIF-8 composite photocatalyst and the preparation method and the application thereof are disclosed, and the preparation method comprises the following steps: heating urea powder at 7-9 deg.C/min and maintaining the temperature to obtain g-C3N4Powder; dispersing in a mixed solution of zinc nitrate and methanol to obtain a mixed solution A; dissolving 2-methylimidazole powder in a methanol solution to obtain a mixed solution B; adding the mixed solution B into the mixed solution A to obtain a mixed solution C, and transferring the mixed solution C into a reaction kettle to perform solvothermal reaction; centrifuging, cleaning, and vacuum drying; the invention adopts the optimal heating speed, so that the volatilized ammonia gas can hinder the sintering and agglomeration tendency of product powder and reach the optimal balance state in the heating and cracking process of the urea, and the flaky g-C is obtained3N4Increase inThe specific surface area of the product is shown; by adopting the solvothermal method, the synthesis time is greatly shortened, and the crystal grain with smaller size, more complete crystal form and more surface reaction active sites can be obtained.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a photocatalystSeed g-C3N4@ ZIF-8 composite photocatalyst and preparation method and application thereof.
Background
Industrial wastewater in the fields of medicine, printing and dyeing, paper making and the like contains a plurality of pollutants which are difficult to degrade and affect human health, and is a major problem of water ecological environment to be solved urgently. The semiconductor photocatalytic material takes solar energy as an energy source, can effectively remove organic pollutants in water under mild reaction conditions, and is one of the most potential technologies for solving energy and environmental problems.
g-C3N4The catalyst has a layered structure similar to graphite, is a common non-metal semiconductor material, has the advantages of no toxicity, small band gap (2.7eV), wide visible light absorption spectrum and the like, and is a novel visible light catalyst which is rapidly developed in recent years. However, a single form of g-C3N4The defects of limited visible light capturing capability, easy recombination of photon-generated carriers and small specific surface area exist, and the actual photocatalytic efficiency is greatly different from the theoretical efficiency.
Zeolite Imidazolate framework materials (ZIFs) are novel Metal Organic Frameworks (MOFs) which take imidazole or a diffractometer thereof as a ligand and have a zeolite topological structure, have the advantages of zeolites and MOFs, and have excellent thermal stability, structural stability and adjustability of structure and function. The ZIF-8 takes metal zinc as a metal ligand of MOFs, has the advantages of large specific surface area, good solvent thermal stability, organic solvent resistance and the like, and is one of ZIFs materials with the greatest photocatalytic potential. However, the single form of ZIF-8 is mainly applied to the fields of gas adsorption, separation, hydrogen storage, catalysis and the like, and the application in the field of photocatalysis is limited because the band gap is large (Eg ≈ 5.1eV), and the optical quantum effect in the visible light region is weak.
Patent publication No. CN103170358A discloses a porous g-C3N4Photocatalyst and preparation method thereof, and porous g-C can be successfully prepared3N4The catalytic efficiency of the obtained catalyst under the condition of visible light can reach more than 65%, and the obtained catalyst shows better photocatalytic performance. But instead of the other end of the tubeThe catalytic efficiency of the photocatalyst is far from the production and living requirements, and the photocatalyst needs to be further modified to improve the visible light catalytic efficiency.
Patent publication No. CN113522330A discloses a magnetic ZIF-8 coated Fe3O4/g-C3N4Composite catalyst, preparation method and application thereof, and magnetic ZIF-8 coated Fe3O4/g-C3N4The composite photocatalyst has a wider spectral response range, higher carrier separation efficiency and photocatalytic activity, and can be separated, recovered and recycled. However, the preparation period is long, the preparation process is complicated, the obtained ZIF-8 has large particles (100-500 mu m), and the ZIF-8 is coated with Fe3O4/g-C3N4The rear structure mode can not give full play to ZIF-8 and g-C3N4The heterojunction formed by the two has limited effective photocatalysis efficiency for the effective transmission of photogenerated carriers.
The patent with the publication number CN110124736A discloses a composite visible-light catalyst ZIF-8@ S-g-C3N4The preparation of (1) thiourea in H2Roasting at 475-550 ℃ for 2-4h in the atmosphere of S to obtain the sulfide layered g-C3N4Then the mixture reacts in ice bath by a stirring method to obtain ZIF-8@ S-g-C3N4. The method adopts a technical process in which H needs to be introduced2S gas, and H2S gas is extremely toxic, so that the whole experiment needs to be carried out in a closed container, the requirements on process equipment are high, and tail gas discharged in the reaction process pollutes the environment; the process adopts a mechanical stirring method, takes long time and is difficult to control the morphology of the catalyst powder.
The patent publication No. CN112090448A discloses ZIF-8@ g-C of zeolite structure3N4The preparation method of the catalyst adopts urea as a raw material to obtain the layered g-C by pyrolysis3N4Then reacting barbituric acid, zinc nitrate and dimethylimidazole at room temperature under the condition of mechanical stirring to obtain ZIF-8@ g-C3N4Also, it takes a long time and it is difficult to control the morphology and structure of ZIF-8, thereby adversely affecting the catalytic efficiency of the catalyst.
Patent publication No. CN111992255A discloses a sheet-like g-C3N4A/ZIF-8/AgBr composite material and a preparation method thereof are disclosed, wherein melamine is adopted as a raw material, and g-C obtained by calcination is adopted3N4Then etching with concentrated sulfuric acid to obtain flake g-C3N4. The concentrated sulfuric acid required in the process severely corrodes equipment, and the volatile gas of the concentrated sulfuric acid has serious adverse effect on the surrounding environment.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide g-C3N4@ ZIF-8 composite photocatalyst and preparation method and application thereof, thereby solving the additional environmental burden brought by the technological process and g-C3N4The theoretical photocatalytic efficiency is difficult to achieve.
In order to achieve the above purpose, the solution of the invention is as follows:
in a first aspect, the present invention provides a g-C3N4The preparation method of the @ ZIF-8 composite photocatalyst comprises the following steps:
(1) heating urea powder at the speed of 7-9 ℃/min, preserving heat, and thermally decomposing to obtain g-C with lamellar microstructure3N4Powder;
(2) magnetically stirring the mixture to obtain g-C3N4The powder is dispersed in zinc nitrate (Zn (NO)3)2·5H2O) and methanol (the concentration is more than 99 percent, the same below) to obtain a mixed solution A;
(3) dissolving 2-methylimidazole powder in a methanol solution to obtain a mixed solution B;
(4) adding the mixed solution B into the mixed solution A under the condition of magnetic stirring, and continuously stirring for 1h to obtain mixed solution C; transferring the mixed solution C into a closed reaction kettle to carry out solvothermal reaction;
(5) naturally cooling to room temperature after the reaction is finished, carrying out centrifugal separation on the mixed solution C to obtain precipitates, respectively washing the white precipitates twice by using a methanol solution and deionized water, and carrying out centrifugal separation and then carrying out next washing after each washing;
(6) vacuum drying the precipitate to obtain g-C3N4@ ZIF-8 composite photocatalyst.
Further, in the step (1), the heating temperature is 500-.
Further, in the step (2), the magnetic stirring speed is 400-600 rpm.
Further, in the step (2), g to C in the mixed solution A3N4Powder, Zn (NO)3)2·5H2The mass ratio of the O to the methanol is 1 (2-3) to 25-30.
Further, in the step (3), the mass ratio of the 2-methylimidazole powder to the methanol in the mixed solution B is (5-7) to (25-30).
Further, in the step (4), the magnetic stirring speed is 400-600 rpm.
Further, in the step (4), the volume ratio of the mixed solution a to the mixed solution B is 1:1.
Further, in the step (4), the temperature of the solvothermal reaction is 145-155 ℃, and the time is 3-6 h.
Further, in the step (5), the rotation speed of the centrifugation is 8000-10000rpm, and the time of the centrifugation is 5-10 min.
Further, in the step (6), the temperature of vacuum drying of the precipitate is 55-65 ℃, the time of vacuum drying is 11-14h, and the vacuum degree is less than 0.01 MPa.
In a second aspect, the present invention provides a g-C3N4@ ZIF-8 composite photocatalyst, which is obtained by the preparation method.
Further, g-C3N4@ ZIF-8 composite photocatalyst with ZIF-8 nano particles uniformly distributed in g-C3N4Forming a heterojunction structure between the two phase interfaces; g-C3N4g-C in @ ZIF-8 composite photocatalyst3N4The mass ratio of the ZIF to the ZIF-8 is 1 (1.2-1.6).
Further, g-C3N4In the @ ZIF-8 composite photocatalyst, the shape of ZIF-8 is a rhombic dodecahedron structure, and the particle size is 50-200 nm.
In a third aspect, the present invention provides a g-C3N4Application of @ ZIF-8 composite photocatalyst, g-C3N4The @ ZIF-8 composite photocatalyst can decompose pollutants in water under natural illumination (specifically visible light), and can effectively improve the photodegradation efficiency and effect.
Due to the adoption of the scheme, the invention has the beneficial effects that:
1. the invention adopts the optimal heating speed to ensure that the volatilized ammonia gas prevents the product from just inhibiting the tendency of powder sintering agglomeration in the heating and cracking process of the urea, thereby obtaining lamellar g-C3N4And (3) powder. The urea can generate ammonia gas and molten liquid substances in the heating and cracking process, and the molten liquid substances form porous fluffy powder due to gas volatilization and rise. If the heating speed is too low, the amount of the volatile gas is not enough, and the powder obtained by decomposition is easy to sinter into a block-shaped substance; when the heating speed is too high, the urea can be completely changed into ammonia gas and carbon dioxide to volatilize because the reaction is too violent, and g-C3N4The yield of the powder is very low; the urea is heated and cracked at the optimal temperature rise speed, and the cracking product g-C with the sheet shape under the microcosmic condition can be obtained3N4The target product with larger specific surface area can be obtained without additional treatment. According to the measurement results of the present invention, the specific surface area of the decomposition product can be changed from bulk g-C with an optimum temperature rise rate3N432.197m2Increase in/g to lamellar structure g-C3N445.4591m2(ii) in terms of/g. The specific surface area of the composite photocatalyst obtained by compounding can be increased to 112.2305m2/g。
2. Synthesis of g-C by solvothermal method3N4Compared with the similar patent disclosed in the invention, the synthesis time is shortened from 12-33h to 4-6h (solvothermal reaction time), and the composite photocatalyst with smaller grain size, more complete crystal form and large surface reaction activity can be obtained, so that the photon quantum efficiency of the catalyst is improved, and a higher photon-generated carrier is obtained under the same illumination condition. By adopting the method, the composite light can be obtainedThe catalyst interface forms a well-combined heterojunction and a II-type heterojunction structure, so that photo-generated electrons (e) are generated on the surface of the photocatalytic material-) And a cavity (h)+) Molecular oxygen (O) effectively separated from the catalyst and adsorbed on the surface of the catalyst2) Reacting with hydroxyl (OH) group or adsorbed water to generate a large amount of superoxide radical (. O)2-) And hydroxyl free radical (. OH) and other catalytic reaction active groups, so that pollutants in water such as methylene blue can be quickly and thoroughly photodegraded under the irradiation of visible light.
3. The raw materials required by the invention are common chemicals, are cheap and easily available, and have simple required process, low equipment requirement, simple process and strong controllability of reaction conditions. In addition, g-C prepared3N4@ ZIF-8 composite photocatalyst with ZIF-8 nano-particles in lamellar g-C3N4The characteristic morphology of in-situ self-growth obviously improves the light quantum efficiency of the catalyst, and has excellent visible light catalytic activity.
Drawings
FIG. 1 shows g-C of example 1 of the present invention3N4The shape graph of the @ ZIF-8 composite photocatalyst is observed by a scanning electron microscope (a) and a transmission electron microscope (b).
FIG. 2 shows g-C of example 3 of the present invention3N4@ ZIF-8 composite photocatalyst and monomer (g-C)3N4ZIF-8).
FIG. 3 is g-C of examples 1 to 4 of the present invention, and comparative examples 1 and 23N4@ ZIF-8 composite photocatalyst and monomer (g-C)3N4ZIF-8) is used for solving the relation graph of the photodegradation reaction time of the methylene blue solution and the degradation rate.
Detailed Description
The invention provides a g-C3N4@ ZIF-8 composite photocatalyst and preparation method and application thereof.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings and the embodiments. It should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: (in this example, the heating rate of the urea powder was 7 ℃/min.)
g-C of the present example3N4The preparation method of the @ ZIF-8 composite photocatalyst comprises the following steps:
(1) heating urea powder to 550 ℃ at the speed of 7 ℃/min, preserving the heat for 120min, and thermally decomposing to obtain g-C with lamellar microstructure3N4A powder;
(2) g-C was stirred by magnetic stirring (magnetic stirring speed 500rpm)3N4The powder is dispersed in Zn (NO)3)2·5H2Mixing O with methanol (with concentration greater than 99% as the same below) to obtain mixed solution A, wherein g-C in the mixed solution A3N4、Zn(NO3)2·5H2The mass ratio of O to methanol is 1:2: 25;
(3) dissolving 2-methylimidazole powder in a methanol solution to obtain a mixed solution B, wherein the mass ratio of 2-methylimidazole to methanol in the mixed solution B is 5: 25;
(4) adding 1 part of the mixed solution B into 1 part of the mixed solution A under the condition of magnetic stirring (600rpm), and continuously stirring for 1 hour to obtain a mixed solution C; transferring the mixed solution C into a closed reaction kettle, and carrying out solvothermal reaction for 5 hours at 150 ℃;
(5) naturally cooling to room temperature after the reaction is finished, centrifugally separating the mixed solution C (the rotating speed of a centrifugal machine is 9000rpm) to obtain precipitates, respectively washing the white precipitates twice by using 99% methanol solution and deionized water, and after each washing, firstly centrifugally separating and then washing the white precipitates again;
(6) vacuum drying the finally obtained precipitate at 60 ℃ for 12h in a vacuum environment with the vacuum degree of less than 0.01MPa to obtain g-C3N4@ ZIF-8 composite photocatalyst, wherein g-C3N4The mass ratio of the ZIF to the ZIF-8 is 1: 1.3.
Subjecting the resulting g-C3N4@ ZIF-8 composite photocatalyst 1.5g dispersed in 3L of methylene blue aqueous solution (concentration of methylene blue is 10mg/L) under visible light (. lamda.)>420nm) is shown in figure 3, and after 30min, the degradation rate of methylene blue reaches 98.6%.
Example 2: (in this example, the heating rate of the urea powder was 8 ℃/min.)
g-C of the present example3N4The preparation method of the @ ZIF-8 composite photocatalyst comprises the following steps:
(1) heating urea powder to 550 ℃ at the speed of 8 ℃/min, preserving the heat for 120min, and thermally decomposing to obtain g-C with lamellar microstructure3N4Powder;
(2) g-C was stirred by magnetic stirring (magnetic stirring speed 500rpm)3N4The powder is dispersed in Zn (NO)3)2·5H2Mixing O and methanol (the concentration is more than 99 percent, the same below) to obtain a mixed solution A, wherein g-C in the mixed solution A3N4、Zn(NO3)2·5H2The mass ratio of O to methanol is 1:2.5: 25;
(3) dissolving 2-methylimidazole powder in a methanol solution to obtain a mixed solution B, wherein the mass ratio of 2-methylimidazole to methanol in the mixed solution B is 6: 25;
(4) adding 1 part of the mixed solution B into 1 part of the mixed solution A under the condition of magnetic stirring (600rpm), and continuously stirring for 1 hour to obtain a mixed solution C; transferring the mixed solution C into a closed reaction kettle, and carrying out solvothermal reaction for 4h at 150 ℃;
(5) naturally cooling to room temperature after the reaction is finished, performing centrifugal separation (the rotation speed of a centrifugal machine is 10000rpm) on the mixed solution C to obtain precipitates, respectively washing the white precipitates twice by using 99% methanol solution and deionized water, and performing centrifugal separation and then cleaning the next time after each cleaning;
(6) vacuum drying the finally obtained precipitate at 60 ℃ for 12h in a vacuum environment with the vacuum degree of less than 0.01MPa to obtain g-C3N4@ ZIF-8 composite photocatalyst, wherein, g-C3N4The mass ratio of the ZIF to the ZIF-8 is 1: 1.5.
Subjecting the resulting g-C3N4@ 3g of ZIF-8 composite photocatalyst was dispersed in 3L of methylene blue aqueous solution (methylene blue concentration: 20mg/L) in visible light (. lamda.) (λ)>420nm), the degradation kinetic curve is shown in figure 3, and after 30min, the degradation rate of methylene blue reaches 93.5%.
Example 3: (in this example, the heating rate of the urea powder was 7 ℃/min.)
g-C of the present example3N4The preparation method of the @ ZIF-8 composite photocatalyst comprises the following steps:
(1) heating urea powder to 550 ℃ at the speed of 7 ℃/min, preserving the heat for 120min, and thermally decomposing to obtain g-C with lamellar microstructure3N4A powder;
(2) stirring the mixture by magnetic stirring (the magnetic stirring speed is 500rpm)3N4The powder is dispersed in Zn (NO)3)2·5H2Mixing O with methanol (with concentration greater than 99% as the same below) to obtain mixed solution A, wherein g-C in the mixed solution A3N4、Zn(NO3)2·5H2The mass ratio of O to methanol is 1:2.5: 30;
(3) dissolving 2-methylimidazole powder in a methanol solution to obtain a mixed solution B, wherein the mass ratio of 2-methylimidazole to methanol in the mixed solution B is 6: 30;
(4) adding 1 part of the mixed solution B into 1 part of the mixed solution A under the condition of magnetic stirring (600rpm), and continuously stirring for 1 hour to obtain a mixed solution C; transferring the mixed solution C into a closed reaction kettle, and carrying out solvothermal reaction for 6h at 150 ℃;
(5) naturally cooling to room temperature after the reaction is finished, centrifugally separating the mixed solution C (the rotating speed of a centrifugal machine is 9000rpm) to obtain precipitates, respectively washing the white precipitates twice by using 99% methanol solution and deionized water, and after each washing, firstly centrifugally separating and then washing the white precipitates again;
(6) vacuum drying the finally obtained precipitate at 60 ℃ for 12h in a vacuum environment with the vacuum degree of less than 0.01MPa to obtain g-C3N4@ ZIF-8 composite photocatalyst, wherein g-C3N4The mass ratio of the ZIF-8 to the ZIF-8 is 1: 1.5.
Subjecting the resulting g-C3N4@ 3g of ZIF-8 composite photocatalyst was dispersed in 3L of methylene blue aqueous solution (the concentration of methylene blue was 10mg/L) in visible light (. lamda.) (λ)>420nm), the degradation kinetic curve is shown in figure 3, and the degradation rate of methylene blue reaches 98.9 percent after 30 min.
Example 4: (in this example, the heating rate of the urea powder was 8 ℃/min.)
g-C of the present example3N4The preparation method of the @ ZIF-8 composite photocatalyst comprises the following steps:
(1) heating urea powder to 550 ℃ at the speed of 8 ℃/min, preserving the heat for 120min, and thermally decomposing to obtain g-C with lamellar microstructure3N4Powder;
(2) g-C was stirred by magnetic stirring (magnetic stirring speed 500rpm)3N4The powder is dispersed in Zn (NO)3)2·5H2Mixing O with methanol (with concentration greater than 99% as the same below) to obtain mixed solution A, wherein g-C in the mixed solution A3N4、Zn(NO3)2·5H2The mass ratio of O to methanol is 1:3: 25;
(3) dissolving 2-methylimidazole powder in a methanol solution to obtain a mixed solution B, wherein the mass ratio of 2-methylimidazole to methanol in the mixed solution B is 6: 30;
(4) adding 1 part of the mixed solution B into 1 part of the mixed solution A under the condition of magnetic stirring (600rpm), and continuously stirring for 1 hour to obtain a mixed solution C; transferring the mixed solution C into a closed reaction kettle, and carrying out solvothermal reaction for 4h at 150 ℃;
(5) naturally cooling to room temperature after the reaction is finished, performing centrifugal separation (the rotation speed of a centrifugal machine is 10000rpm) on the mixed solution C to obtain precipitates, respectively washing the white precipitates twice by using 99% methanol solution and deionized water, and performing centrifugal separation and then cleaning the next time after each cleaning;
(6) vacuum drying the finally obtained precipitate at 60 ℃ for 12h in a vacuum environment with the vacuum degree of less than 0.01MPa to obtain g-C3N4@ZIF-8 composite photocatalyst, wherein, g-C3N4The mass ratio of the ZIF-8 to the ZIF-8 is 1: 1.6.
Subjecting the resulting g-C3N4@ 3g of ZIF-8 composite photocatalyst was dispersed in 3L of methylene blue aqueous solution (methylene blue concentration: 20mg/L) in visible light (. lamda.) (λ)>420nm), the degradation kinetic curve is shown in figure 3, and after 30min, the degradation rate of methylene blue reaches 94.8%.
Comparative example 1: (the heating rate of the urea powder in this comparative example was 5 ℃/min)
The process steps used were the same as in example 1 except that the rate of thermal cracking of urea was different.
g-C of this comparative example3N4The preparation method of the @ ZIF-8 composite photocatalyst comprises the following steps:
(1) heating urea powder to 550 ℃ at the speed of 5 ℃/min, preserving the heat for 120min, and thermally decomposing to obtain g-C of an agglomeration curled lamellar sheet microstructure3N4Powder;
(2) g-C was stirred by magnetic stirring (magnetic stirring speed 500rpm)3N4The powder is dispersed in Zn (NO)3)2·5H2Mixing O with methanol (with concentration greater than 99% as the same below) to obtain mixed solution A, wherein g-C in the mixed solution A3N4、Zn(NO3)2·5H2The mass ratio of O to methanol is 1:2: 25;
(3) dissolving 2-methylimidazole powder in a methanol solution to obtain a mixed solution B, wherein the mass ratio of 2-methylimidazole to methanol in the mixed solution B is 5: 25;
(4) adding 1 part of the mixed solution B into 1 part of the mixed solution A under the condition of magnetic stirring (600rpm), and continuously stirring for 1 hour to obtain a mixed solution C; transferring the mixed solution C into a closed reaction kettle, and carrying out solvothermal reaction for 4h at 150 ℃;
(5) naturally cooling to room temperature after the reaction is finished, centrifugally separating the mixed solution C (the rotating speed of a centrifugal machine is 9000rpm) to obtain precipitates, respectively washing the white precipitates twice by using 99% methanol solution and deionized water, and after each washing, firstly centrifugally separating and then washing the white precipitates again;
(6) vacuum drying the finally obtained precipitate at 60 ℃ for 12h in a vacuum environment with the vacuum degree of less than 0.01MPa to obtain g-C3N4@ ZIF-8 composite photocatalyst, wherein g-C3N4The mass ratio of the ZIF-8 to the ZIF-8 is 1: 1.3.
Subjecting the resulting g-C3N4@ ZIF-8 composite photocatalyst 1.5g dispersed in 3L of methylene blue aqueous solution (concentration of methylene blue is 10mg/L) under visible light (. lamda.)>420nm), the degradation kinetic curve is shown in figure 3, and after 30min, the degradation rate of methylene blue reaches 78.1%.
Comparative example 2: (in this comparative example, the heating rate of the urea powder was 8 ℃/min, and the solvothermal method was not employed)
The procedures and process parameters used were the same as in example 2, except that the solvothermal method in step (4) was changed to a room-temperature stirring method.
g-C of this comparative example3N4The preparation method of the @ ZIF-8 composite photocatalyst comprises the following steps:
(1) heating urea powder to 550 ℃ at the speed of 8 ℃/min, preserving the heat for 120min, and thermally decomposing to obtain g-C with lamellar microstructure3N4Powder;
(2) stirring the mixture by magnetic stirring (the magnetic stirring speed is 500rpm)3N4The powder is dispersed in Zn (NO)3)2·5H2Mixing O with methanol (with concentration greater than 99% as the same below) to obtain mixed solution A, wherein g-C in the mixed solution A3N4、Zn(NO3)2·5H2The mass ratio of O to methanol is 1:2.5: 25;
(3) dissolving 2-methylimidazole powder in a methanol solution to obtain a mixed solution B, wherein the mass ratio of 2-methylimidazole to methanol in the mixed solution B is 6: 25;
(4) adding 1 part of the mixed solution B into 1 part of the mixed solution A under the condition of magnetic stirring (600rpm), and continuously stirring for 12 hours at 25 +/-2 ℃ to obtain a mixed solution C;
(5) after the reaction is finished, carrying out centrifugal separation on the mixed solution C (the rotating speed of a centrifugal machine is 10000rpm) to obtain precipitates, respectively washing the white precipitates twice by using 99% methanol solution and deionized water, and after each washing, carrying out centrifugal separation firstly and then carrying out next washing;
(6) vacuum drying the finally obtained precipitate at 60 ℃ for 12h in a vacuum environment with the vacuum degree of less than 0.01MPa to obtain g-C3N4@ ZIF-8 composite photocatalyst, wherein g-C3N4The mass ratio of the ZIF to the ZIF-8 is 1: 1.5.
Subjecting the resulting g-C3N4@ 3g of ZIF-8 composite photocatalyst was dispersed in 3L of methylene blue aqueous solution (methylene blue concentration: 20mg/L) in visible light (. lamda.) (λ)>420nm), the degradation kinetic curve is shown in figure 3, and the degradation rate of methylene blue reaches 72.7 percent after 30 min.
Comparative example 3: (the heating rate of the urea powder in this comparative example was 11 ℃/min.)
Heating urea powder at a speed of 11 deg.C/min to 550 deg.C, and maintaining the temperature for 120 min. As a result, the urea is completely decomposed into ammonia gas and carbon dioxide in the high-speed heating process and volatilized into the air due to the excessive high heating speed, and finally, no g-C is left in the crucible3N4And (3) powder.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments. Those skilled in the art should appreciate that many modifications and variations are possible in light of the above teaching without departing from the scope of the invention.
Claims (10)
1. g-C3N4A preparation method of a @ ZIF-8 composite photocatalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) heating urea powder at the speed of 7-9 ℃/min, preserving heat, and performing thermal decomposition to obtain g-C with lamellar structure3N4Powder;
(2) stirring the g-C by magnetic force3N4Dispersing the powder in a mixed solution of zinc nitrate and methanol to obtain a mixed solution A;
(3) dissolving 2-methylimidazole powder in a methanol solution to obtain a mixed solution B;
(4) adding the mixed solution B into the mixed solution A under the condition of magnetic stirring, and continuously stirring to obtain mixed solution C; transferring the mixed solution C into a closed reaction kettle to carry out solvothermal reaction;
(5) cooling to room temperature after the reaction is finished, carrying out centrifugal separation on the mixed solution C to obtain precipitates, respectively washing with a methanol solution and deionized water, centrifuging after washing, and then washing;
(6) vacuum drying the precipitate to obtain the g-C3N4@ ZIF-8 composite photocatalyst.
2. g-C according to claim 13N4The preparation method of the @ ZIF-8 composite photocatalyst is characterized by comprising the following steps of: in the step (1), the heating temperature is 500-600 ℃, and the heat preservation time is 100-130 min.
3. g-C according to claim 13N4The preparation method of the @ ZIF-8 composite photocatalyst is characterized by comprising the following steps of: in the step (2), the magnetic stirring speed is 400-600 rpm.
4. g-C according to claim 13N4The preparation method of the @ ZIF-8 composite photocatalyst is characterized by comprising the following steps of: in the step (2), g-C in the mixed solution A3N4The mass ratio of the powder to the zinc nitrate to the methanol is 1 (2-3) to 25-30.
5. g-C according to claim 13N4The preparation method of the @ ZIF-8 composite photocatalyst is characterized by comprising the following steps of: in the step (3), the substances of the 2-methylimidazole powder and the methanol in the mixed solution BThe quantity ratio is (5-7) to (25-30).
6. g-C according to claim 13N4The preparation method of the @ ZIF-8 composite photocatalyst is characterized by comprising the following steps of: in the step (4), the magnetic stirring speed is 400-600 rpm; and/or the presence of a gas in the gas,
in the step (4), the volume ratio of the mixed solution A to the mixed solution B is 1: 1; and/or the presence of a gas in the gas,
in the step (4), the temperature of the solvothermal reaction is 145-155 ℃, and the time is 3-6 h; and/or the presence of a gas in the gas,
in the step (5), the rotation speed of the centrifugation is 8000-10000rpm, and the centrifugation time is 5-10 min.
7. g-C according to claim 13N4The preparation method of the @ ZIF-8 composite photocatalyst is characterized by comprising the following steps of: in the step (6), the temperature of vacuum drying of the precipitate is 55-65 ℃, the time of vacuum drying is 11-14h, and the vacuum degree is less than 0.01 MPa.
8. g-C3N4@ ZIF-8 composite photocatalyst, its characterized in that: which is obtained by the production method according to any one of claims 1 to 7.
9. g-C according to claim 83N4@ ZIF-8 composite photocatalyst, its characterized in that: the g to C3N4In the @ ZIF-8 composite photocatalyst, ZIF-8 is uniformly distributed in g-C3N4Forming a heterojunction structure on the surface; the g to C3N4g-C in @ ZIF-8 composite photocatalyst3N4The mass ratio of the ZIF-8 to the ZIF-1 is 1 (1.2-1.6); and/or the presence of a gas in the gas,
the g to C3N4The shape of ZIF-8 in the @ ZIF-8 composite photocatalyst is a rhombic dodecahedron structure, and the particle size is 50-200 nm.
10. A composition of g-C as claimed in claim 83N4The application of the @ ZIF-8 composite photocatalyst is characterized in that: the g to C3N4The application of the @ ZIF-8 composite photocatalyst in degrading pollutants in water under natural illumination is disclosed.
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