CN113663704B - Indium zinc sulfide/graphite phase carbon nitride composite material and preparation and application thereof - Google Patents
Indium zinc sulfide/graphite phase carbon nitride composite material and preparation and application thereof Download PDFInfo
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- CN113663704B CN113663704B CN202110819755.4A CN202110819755A CN113663704B CN 113663704 B CN113663704 B CN 113663704B CN 202110819755 A CN202110819755 A CN 202110819755A CN 113663704 B CN113663704 B CN 113663704B
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- phase carbon
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 60
- UDWJTDBVEGNWAB-UHFFFAOYSA-N zinc indium(3+) sulfide Chemical compound [S-2].[Zn+2].[In+3] UDWJTDBVEGNWAB-UHFFFAOYSA-N 0.000 title claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 44
- 239000010439 graphite Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002135 nanosheet Substances 0.000 claims abstract description 26
- 230000001699 photocatalysis Effects 0.000 claims abstract description 22
- 238000004659 sterilization and disinfection Methods 0.000 claims abstract description 17
- 230000001954 sterilising effect Effects 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000007146 photocatalysis Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 5
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 5
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 38
- 230000000694 effects Effects 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 239000011941 photocatalyst Substances 0.000 abstract description 5
- 239000010865 sewage Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- UKCIUOYPDVLQFW-UHFFFAOYSA-K indium(3+);trichloride;tetrahydrate Chemical compound O.O.O.O.Cl[In](Cl)Cl UKCIUOYPDVLQFW-UHFFFAOYSA-K 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- YYKKIWDAYRDHBY-UHFFFAOYSA-N [In]=S.[Zn] Chemical compound [In]=S.[Zn] YYKKIWDAYRDHBY-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- -1 carbon nitride compound Chemical class 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000034994 death Effects 0.000 description 1
- 231100000517 death Toxicity 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
- 238000001514 detection method Methods 0.000 description 1
- ZAASRHQPRFFWCS-UHFFFAOYSA-P diazanium;oxygen(2-);uranium Chemical compound [NH4+].[NH4+].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[U].[U] ZAASRHQPRFFWCS-UHFFFAOYSA-P 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B01J35/39—
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/027—Preparation from water
-
- 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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- 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
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
-
- 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
Abstract
The invention belongs to the technical field of new energy materials, and particularly relates to an indium zinc sulfide/graphite phase carbon nitride composite material and preparation and application thereof, which are applied to in-situ production of hydrogen peroxide for sterilization, in particular to sewage sterilization, wherein the preparation method of the indium zinc sulfide/graphite phase carbon nitride composite material comprises the following steps: dispersing graphite-phase carbon nitride nano-sheets into a solvent containing an indium zinc sulfide precursor, and heating and reacting to obtain the indium zinc sulfide/graphite-phase carbon nitride composite material. The preparation method is simple, and raw materials are easy to obtain; the prepared indium zinc sulfide/graphite phase carbon nitride composite material is a photocatalyst with excellent performance, has high efficiency and good stability in producing hydrogen peroxide by photocatalysis, has good sterilization and disinfection effects, and is favorable for recycling and reutilizing the photocatalyst.
Description
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to an indium zinc sulfide/graphite phase carbon nitride composite material, and preparation and application thereof, which are applied to in-situ hydrogen peroxide production for sterilization, in particular to sewage sterilization.
Background
Despite the highly developed medical technology, bacterial infection in sewage remains one of the major health threats facing humans, leading to millions of patient deaths each year. Due to the influence of bacterial drug resistance, the environment-friendly photoelectric material is expected to become an alternative strategy of antibiotics. Among them, the photocatalysis technology attracts attention of many researchers due to the advantages of low toxicity, mildness, low cost, high efficiency and the like.
Hydrogen peroxide (H) 2 O 2 ) As an environment-friendly oxidant, the catalyst is widely applied to the fields of organic synthesis, wastewater treatment, medical disinfection and the like. At the same time H 2 O 2 Only water and oxygen are produced during medical disinfection, and no secondary oxygen is producedSecondary infection. Due to H at normal temperature and pressure 2 O 2 The fuel cell is in a liquid state, has the advantages of being dissolved in water, being used for sterilization, disinfection, convenient storage and transportation and the like, and is also widely paid attention to as a fuel cell energy carrier for replacing hydrogen. Currently, the anthraquinone process is mainly used in industrial production to produce H on a large scale 2 O 2 But the high energy consumption due to the multi-step hydrogenation and oxidation reactions is a synthetic method with non-green features. In addition, there are catalysts using noble metals and their alloys to convert H 2 (g) And O 2 (g) Direct synthesis of H 2 O 2 But due to the inclusion of H 2 /O 2 The gases of the mixture are explosive and therefore present a certain risk. Scientists are therefore always exploring an efficient, green, economical H 2 O 2 The synthesis method, in which semiconductor photocatalysis is attractive because of the advantages of cleanliness, one-step synthesis, environmental friendliness and the like. However, to date, H has been synthesized on a large scale using solar energy 2 O 2 But also challenges.
Preparation of H in photocatalysis 2 O 2 In the field, graphite-phase carbon nitride materials with better photocatalytic activity stand out, however, the graphite-phase carbon nitride materials have more defects, such as narrower absorption range and weaker absorption strength for visible light, faster recombination rate of photo-generated electrons and holes, lower carrier mobility and the like, which greatly limit the preparation of H under the action of visible light 2 O 2 Is a performance of the (c). In recent years, it has been found that the above-mentioned disadvantages can be overcome by the construction of a heterojunction. Zinc indium sulfide, in the photocatalytic reduction of CO 2 And hydrogen production, have attracted considerable attention due to their good electrical conductivity and strong absorption of visible light. Therefore, in-situ growth of indium zinc sulfide on the surface of graphite-phase carbon nitride photocatalyst to promote H generation 2 O 2 The efficiency of (2) and achieving the sterilization and disinfection effects are important points of research.
Disclosure of Invention
The invention aims to provide an indium zinc sulfide/graphite phase carbon nitride composite material and a preparation method thereof, which are used for sterilizing hydrogen peroxide produced in situ under sunlight irradiation, particularly sterilizing sewage, and have the advantages of higher hydrogen peroxide production efficiency and sterilizing capability, greenness, economy and the like.
According to the technical scheme of the invention, the preparation method of the indium zinc sulfide/graphite phase carbon nitride composite material comprises the following steps: dispersing graphite-phase carbon nitride nano-sheets into a solvent containing an indium zinc sulfide precursor, and heating and reacting to obtain the indium zinc sulfide/graphite-phase carbon nitride composite material.
According to the invention, the indium zinc sulfide nano-sheets are grown on the surface of the graphite-phase carbon nitride nano-sheets, so that the surface area is increased, the morphology structure of the compound is regulated and controlled by controlling the adding amount of the indium zinc sulfide, the adding amount of the indium zinc sulfide is large, the attached nano-sheets are dense, the adding amount is small, and the small nano-sheets on the surface are sparse.
Further, the mass ratio of the indium zinc sulfide to the graphite phase carbon nitride is 0.1-1.5:1.
further, the graphite-phase carbon nitride nano-sheet is obtained by taking a carbon nitride compound as a precursor and calcining.
Further, the preparation method of the graphite phase carbon nitride nano-sheet comprises the following steps:
a. calcining the carbon nitrogen compound at 200-550 ℃ for 1-5 hours to obtain a block;
b. grinding the mass into a powder;
c. calcining the powder for 1-3 hours at the temperature of 200-550 ℃ to obtain the graphite phase carbon nitride nano-sheet.
Further, the carbon-nitrogen compound is one or more of dicyandiamide, urea, thiourea, cyanamide, melamine and the like.
Further, the indium zinc sulfide precursor is zinc chloride, indium chloride and thioacetamide, and the solvent is a mixed solution of water and glycerin with pH of 1-5.
Specifically, in the indium zinc sulfide precursor, the molar ratio of zinc chloride to indium chloride to thioacetamide is 1:1.5-2.5:3-5, preferably 1:2:4, a step of; in the solvent, the volume ratio of water to glycerol is 8-12:3, preferably 10:3.
further, the heating is hydrothermal heating, the heating temperature is 60-120 ℃ and the heating time is 1.5-3h.
Specifically, the preparation method of the indium zinc sulfide/graphite phase carbon nitride composite material can be as follows: placing a precursor of indium zinc sulfide into a solution with pH=1-5 (preferably 2.5), adding graphite-phase carbon nitride nano-sheets, performing ultrasonic dispersion, and heating in an oil bath at 60-120 ℃ for 1.5-3h; centrifuging the heated solution, washing the centrifuged precipitate with water and ethanol for multiple times (3-6), and vacuum drying at 50-70 ℃ to obtain the solution of the indium zinc sulfide/graphite phase carbon nitride composite material.
According to the method, the indium zinc sulfide nano-sheets can be successfully modified on the surface of the graphite phase carbon nitride nano-sheets, and the indium zinc sulfide/graphite phase carbon nitride nano-sheets which are uniformly distributed are found, so that a perfect heterojunction structure is formed, and the method plays a vital role in improving the efficiency of producing hydrogen peroxide by photocatalysis.
According to the preparation method, a carbon nitrogen compound (such as dicyandiamide) is used as a raw material, a graphite-phase carbon nitride nano sheet is prepared by secondary calcination, and then an indium zinc sulfide nano sheet is modified to the surface of the graphite-phase carbon nitride nano sheet by a hydrothermal method, so that a perfect heterojunction structure is formed. The composite material has strong absorption capacity to visible light due to the introduction of the indium zinc sulfide, has proper band gap and good conductivity, and can greatly improve the photocatalysis performance.
The second aspect of the invention provides the indium zinc sulfide/graphite phase carbon nitride composite material prepared by the preparation method. The composite material has high visible light absorption capacity due to excellent visible light response and high carrier mobility, and has high hydrogen peroxide production efficiency and sterilization capacity.
The third aspect of the invention provides application of the indium zinc sulfide/graphite phase carbon nitride composite material in photocatalytic preparation of hydrogen peroxide and photocatalytic sterilization, wherein the photocatalytic sterilization is particularly used for preparing hydrogen peroxide in situ for sterilization, and particularly used for sterilizing and purifying sewage.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the preparation method of the indium zinc sulfide/graphite phase carbon nitride composite material is simple, raw materials are easy to obtain, the operation is simple and convenient, and the preparation method is very critical to industrial application.
2. According to the invention, the surface area of the indium zinc sulfide/graphite phase carbon nitride structure can be increased by controlling the structure, so that the efficiency of producing hydrogen peroxide by photocatalysis is improved; the introduction of the indium zinc sulfide can greatly improve the electron transmission efficiency, increase the absorption range of visible light, improve the utilization rate of graphite phase carbon nitride to the visible light and further improve the hydrogen peroxide production efficiency by photocatalysis.
3. The indium zinc sulfide/graphite phase carbon nitride composite material is a photocatalyst with excellent performance, has high efficiency and good stability in producing hydrogen peroxide by photocatalysis, has good sterilization effect, and is favorable for recycling and reutilization of the photocatalyst.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) of graphite phase carbon nitride;
FIG. 2 is a Transmission Electron Microscope (TEM) of graphite phase carbon nitride;
FIG. 3 is a scanning electron microscope image of indium zinc sulfide;
FIG. 4 is a transmission electron microscope image of indium zinc sulfide;
FIG. 5 is a scanning electron microscope image of an indium zinc sulfide/graphite phase carbon nitride composite material;
FIGS. 6 and 7 are transmission electron microscopy images of indium zinc sulfide/graphite phase carbon nitride composites;
FIG. 8 is a graph showing the effect of photocatalytic hydrogen peroxide generation;
FIG. 9 is a graph of the effect of a cycle of photocatalytic hydrogen peroxide generation;
FIG. 10 is a graph showing the effect of the photocatalytic material on killing E.coli.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Example 1: preparation of indium zinc sulfide nanosheets
20mL of water and 6mL of glycerol were injected into a round bottom flask, the pH of the solution was adjusted to 2.5 with hydrochloric acid, and the solution was sonicated to give a homogeneous solution. Subsequently, 27.2mg of zinc chloride, 117.2mg of indium chloride tetrahydrate and 60mg of thioacetamide were added to the above solution, stirred for 30min, and heated at 80℃for two hours. Centrifuging the reacted product, washing the centrifuged precipitate with water and ethanol for multiple times, and vacuum drying at 50-70 ℃ to obtain yellow indium zinc sulfide nanosheet powder.
Fig. 3 and fig. 4 are SEM images and TEM images of indium zinc sulfide, respectively, and it can be seen from the images that pure indium zinc sulfide presents a nano-flower structure.
Example 2: preparation of graphite phase carbon nitride nano-sheet
10g dicyandiamide is placed in a covered crucible and is directly calcined in a muffle furnace, the heating rate is 2.3 ℃/min, the calcining temperature is 550 ℃, and the calcining time is 4 hours. Dark yellow cake g-C was obtained 3 N 4 Then ground to a dark yellow powder. And (3) placing a small amount of dark yellow powder into a porcelain boat, heating to 550 ℃ at a heating rate of 5 ℃/min, and calcining for 2 hours. Finally obtaining yellowish graphite phase carbon nitride nano-sheet powder.
Fig. 1 and 2 are SEM images and TEM images of graphite-phase carbon nitride, respectively, from which it can be observed that the prepared graphite-phase carbon nitride exhibits a lamellar structure.
Example 3: preparation of indium zinc sulfide/graphite phase carbon nitride composite material
20mL of water and 6mL of glycerol were injected into a round bottom flask, the pH of the solution was adjusted to 2.5 with 0.5M hydrochloric acid, and the solution was sonicated for 3min to disperse it uniformly. Subsequently, 27.2mg of zinc chloride, 117.2mg of indium chloride tetrahydrate and 60mg of thioacetamide were added to the above suspension, stirred for 30 minutes, and graphite-phase carbon nitride nano-sheets (obtained in example 2) of different masses (indium zinc sulfide/graphite-phase carbon nitride mass ratios of 0.1:1, 0.5:1, 1.0:1, 1.5:1, respectively) were further added, stirred for 30 minutes, and heated at 80℃for two hours. After the reaction is finished, centrifugally separating the product, washing the product three times by water and ethanol respectively, and finally drying in a vacuum oven at 65 ℃ to obtain the indium zinc sulfide/graphite phase carbon nitride composite material.
Fig. 5 and fig. 6-7 are SEM images and TEM images of the indium zinc sulfide/graphite phase carbon nitride composite material, respectively, from which it can be clearly and intuitively seen that the indium zinc sulfide nano-sheet is successfully modified to the surface of the graphite phase carbon nitride nano-sheet, and a perfect heterojunction structure is formed.
Detection examples
20mg of the indium zinc sulfide/graphite phase carbon nitride composite material prepared in example 3, 45mL of deionized water and 5mL of isopropanol are uniformly mixed, then the mixture is placed into a photocatalytic reactor, stirred for 10min, condensed water is introduced, and a xenon lamp light source is turned on to start photocatalytic reaction.
By adding isopropanol as a sacrificial agent, acetone is generated by oxidation reaction at the hole, recombination of electrons and holes is prevented, the efficiency of producing hydrogen peroxide by photocatalysis reaction is improved, and ethanol, furfuryl alcohol, methanol and the like can be adopted as the sacrificial agent.
Fig. 8 and 9 are graphs of the effect of photocatalytic hydrogen peroxide production and the cyclic effect of hydrogen peroxide production of the indium zinc sulfide/graphite phase carbon nitride composite material, respectively. From the graph, the efficiency of the indium zinc sulfide/graphite phase carbon nitride composite material for catalyzing and producing hydrogen peroxide is obviously better than that of pure graphite phase carbon nitride material and pure indium zinc sulfide material, and the composite material has good stability.
FIG. 10 is a graph showing the effect of the indium zinc sulfide/graphite phase carbon nitride composite material on killing Escherichia coli by photocatalysis. The graph shows that the indium zinc sulfide/graphite phase carbon nitride composite material can completely kill escherichia coli after 40min of illumination, and has a good sterilization effect.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (2)
1. The application of the indium zinc sulfide/graphite phase carbon nitride composite material in photocatalysis sterilization is that the indium zinc sulfide/graphite phase carbon nitride composite material is prepared by dispersing graphite phase carbon nitride nano-sheets into a solvent containing an indium zinc sulfide precursor and heating and reacting, wherein the mass ratio of the indium zinc sulfide to the graphite phase carbon nitride in the indium zinc sulfide/graphite phase carbon nitride composite material is 0.1-1.5:1, a step of;
the preparation method of the graphite phase carbon nitride nanosheets comprises the following steps:
a. calcining the carbon nitrogen compound at 200-550 ℃ for 1-5 hours to obtain a block;
b. grinding the mass into a powder;
c. calcining the powder at 200-550 ℃ for 1-3 hours to obtain the graphite phase carbon nitride nano-sheet;
the indium zinc sulfide precursor is zinc chloride, indium chloride and thioacetamide, and the solvent is a mixed solution of water and glycerol;
the heating is hydrothermal heating, the heating temperature is 60-120 ℃ and the heating time is 1.5-3h.
2. The use according to claim 1, wherein the carbon nitrogen compound is one or more of dicyandiamide, urea, thiourea, mono-cyanamide and melamine.
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