CN115254165A - Carbon nitride-sulfur indium zinc heterogeneous material and preparation method and application thereof - Google Patents
Carbon nitride-sulfur indium zinc heterogeneous material and preparation method and application thereof Download PDFInfo
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- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 57
- 239000011593 sulfur Substances 0.000 title claims abstract description 57
- NJWNEWQMQCGRDO-UHFFFAOYSA-N indium zinc Chemical compound [Zn].[In] NJWNEWQMQCGRDO-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 41
- 229910052799 carbon Inorganic materials 0.000 title claims description 40
- 239000002243 precursor Substances 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000003756 stirring Methods 0.000 claims abstract description 40
- YYKKIWDAYRDHBY-UHFFFAOYSA-N [In]=S.[Zn] Chemical compound [In]=S.[Zn] YYKKIWDAYRDHBY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000001699 photocatalysis Effects 0.000 claims abstract description 19
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001338 self-assembly Methods 0.000 claims abstract description 6
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 4
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 32
- 239000012153 distilled water Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 150000002471 indium Chemical class 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- 238000010981 drying operation Methods 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 2
- JKNHZOAONLKYQL-UHFFFAOYSA-K tribromoindigane Chemical compound Br[In](Br)Br JKNHZOAONLKYQL-UHFFFAOYSA-K 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 230000032900 absorption of visible light Effects 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 description 12
- UKCIUOYPDVLQFW-UHFFFAOYSA-K indium(3+);trichloride;tetrahydrate Chemical compound O.O.O.O.Cl[In](Cl)Cl UKCIUOYPDVLQFW-UHFFFAOYSA-K 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- HHDOORYZQSEMGM-UHFFFAOYSA-L potassium;oxalate;titanium(4+) Chemical compound [K+].[Ti+4].[O-]C(=O)C([O-])=O HHDOORYZQSEMGM-UHFFFAOYSA-L 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- UDWJTDBVEGNWAB-UHFFFAOYSA-N zinc indium(3+) sulfide Chemical compound [S-2].[Zn+2].[In+3] UDWJTDBVEGNWAB-UHFFFAOYSA-N 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
- 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
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- 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
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Abstract
The invention relates to the technical field of photocatalytic materials, and particularly provides a carbon nitride/sulfur indium zinc heterostructure material, a preparation method and application thereof, wherein the method comprises the steps of taking a precursor formed by self-assembly of melamine and phosphorous acid as a template, and growing a layer of flaky sulfur indium zinc on the precursor by a water bath stirring method; and polymerizing the precursor with the flaky sulfur indium zinc into tubular carbon nitride by a high-temperature calcination method to obtain the carbon nitride/sulfur indium zinc heterogeneous material. The preparation method is simple and easy to operate. The prepared carbon nitride/sulfur indium zinc heterostructure has a unique tubular structure, can promote absorption of visible light and separation of photo-generated charges, and has excellent photocatalysis H generation2O2Good stability. The prepared carbon nitride/sulfur indium zinc heterostructure is used for producing H by photocatalysis2O2Can effectively increase H in the reaction2O2And (4) yield.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a carbon nitride-sulfur indium zinc heterogeneous material and a preparation method and application thereof.
Background
Hydrogen peroxide (chemical formula H)2O2) Is an inorganic compound which can be mixed and dissolved with water in any proportion, is a strong oxidant and is widely used in the industries of organic synthesis, sewage treatment, paper making and the like. And, H2O2Is also considered to replace hydrogen (H)2) The ideal energy carrier. This is because of the reaction with H2Phase contrast H2O2Easier to store and transport. At present, H is produced2O2The most important method is anthraquinone oxidation, 2-ethyl anthraquinone is used as a hydrogenation carrier, and H is finally produced through multi-step hydrogenation and oxidation reactions2O2. However, this method not only consumes a lot of energy, but also has a great influence on the environment. So developing an energy-saving and environmentally friendly process for producing H2O2Is of critical importance.
Recently, H has been produced by semiconductor photocatalytic technology2O2Has shown great prospect, does not produce pollution in the whole reaction process, and is safe and green H2O2A production method. Wherein the graphite phase carbon nitride (g-C)3N4) The photocatalyst is an organic polymer semiconductor photocatalyst which is metal-free and easy to prepare, attracts attention, and has the advantages of corresponding visible light, easy adjustment of electronic structure, environmental friendliness and the like. However, due to g-C3N4Inherent low specific surface area and too fast recombination of photogenerated carriers, causing H2O2The yield of (A) is far from the level required for practical use.
Disclosure of Invention
In order to solve the technical problems, the invention provides a carbon nitride/sulfur indium zinc heterostructure material, and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a carbon nitride-sulfur indium zinc heterogeneous material, which comprises the steps of taking a precursor formed by self-assembly of melamine and phosphorous acid as a template, and growing a layer of flaky sulfur indium zinc on the precursor by a water bath stirring method; and polymerizing the precursor with the flaky sulfur indium zinc into tubular carbon nitride by a high-temperature calcination method to obtain the carbon nitride/sulfur indium zinc heterogeneous material.
Further, the method specifically comprises the following steps: (1) Adding melamine into distilled water at the temperature of 60-100 ℃, stirring for 20-50 min, adding solid phosphorous acid, and continuously stirring for 40-80 min to obtain a mixture; (2) Transferring the mixture into a reaction kettle for heating reaction, and then performing centrifugal operation and drying operation to obtain a precursor; (3) Adding the precursor into distilled water, adjusting the pH value, adding indium salt and zinc salt, stirring for 60-180 min, adding a sulfur source, continuously stirring for 10-40 min, finally putting the reaction system into a water bath, heating in a water bath, stirring for 60-180 min, performing centrifugal operation, and collecting to obtain the precursor with the flaky sulfur indium zinc; (4) And washing and drying the precursor on which the flaky sulfur indium zinc grows, and calcining the precursor in a tubular furnace to obtain the carbon nitride-sulfur indium zinc heterogeneous material.
Further, in the step (1), the mass ratio of the melamine to the solid phosphorous acid is 1.
Further, in the step (2), the heating reaction temperature is 160-200 ℃, and the heat preservation time is 8-12 h; the rotating speed of the centrifugal operation is 3000 r/min-5000 r/min, and the time is 2 min-5 min; the temperature of the drying operation is 40-80 ℃, and the time is 6-12 h.
Further, in the step (3), adjusting the pH to 1-3; the mass ratio of the precursor to the indium salt is 1.059-0.23, the molar ratio of the indium salt to the zinc salt is 1-3; the temperature of the water bath heating is 60-100 ℃.
Further, in the step (3), the indium salt is one or more of indium bromide, indium nitrate and indium chloride; the zinc salt is one or more of zinc acetate, zinc nitrate and zinc chloride; the rotating speed of the centrifugal operation is 3000 r/min-5000 r/min, and the time is 2 min-5 min.
Further, in the step (4), the drying conditions are: the drying temperature is 40-80 ℃, and the drying time is 6-12 h.
The invention provides a carbon nitride-sulfur indium zinc heterogeneous material, and the carbon nitride-sulfur indium zinc heterogeneous material is prepared by the preparation method of the carbon nitride-sulfur indium zinc heterogeneous material.
Further, the heterogeneous material is of a tubular carbon nitride-sulfur indium zinc core-shell structure.
The third aspect of the invention provides the carbon nitride-sulfur indium zinc heterogeneous material for producing H in photocatalysis2O2The use of (1).
Compared with the prior art, the technical scheme provided by the invention at least has the following advantages:
the invention provides a carbon nitride-sulfur indium zinc heterostructure material and a preparation method and application thereof, the preparation method takes a hexagonal rod-shaped supermolecule precursor formed by self-assembling melamine and phosphorous acid as a template, and a layer of flaky sulfur indium zinc grows on the precursor by a water bath stirring method; polymerizing the precursor with the flaky sulfur indium zinc into tubular carbon nitride by a high-temperature calcination method to obtain hexagonal tubular C3N4The carbon nitride/sulfur indium zinc heterogeneous material is a basic framework and grows ZIS nanosheets on the surface, and the preparation method is simple and easy to operate. The prepared carbon nitride/sulfur indium zinc heterostructure has a unique tubular structure, can promote absorption of visible light and separation of photo-generated charges, and has excellent photocatalysis H generation2O2Good stability. The prepared carbon nitride-sulfur indium zinc heterostructure is used for producing H by photocatalysis2O2Can effectively increase H in the reaction2O2And (4) yield.
Drawings
One or more embodiments are illustrated by corresponding figures in the drawings, which are not to be construed as limiting the embodiments, unless expressly stated otherwise, and the drawings are not to scale.
FIG. 1 is a scanning electron microscope image of a precursor in example 1;
fig. 2 is a scanning electron microscope image of the precursor of example 2 with flaky indium zinc sulfide grown thereon;
FIG. 3 is a scanning electron microscope image of the carbon nitride/ZnSInZn heterogeneous material in example 2;
FIG. 4 is a projection electron microscope image of the carbon nitride-sulfur indium zinc heterogeneous material in example 2;
FIG. 5 shows the carbon nitride-sulfur indium zinc heterogeneous material of examples 1, 2, 3 and 4 and ZIn of comparative example2S4/g-C3N4The photocatalytic performance map of (1).
Detailed Description
As is known in the art, g-C is currently used3N4Preparation of H as photocatalyst2O2There is a problem that the yield is low. While the heterojunction strategy is considered to be an effective strategy for improving the photocatalytic efficiency of semiconductors, the construction of the heterojunction is beneficial to promoting the separation of photo-generated charges. The inventor finds that ZnIn2S4The (ZIS) is a ternary metal sulfide semiconductor material, and has the advantages of unique layered structure, proper energy band position, relatively stable photocatalytic performance and the like. And the ZIS nanosheet can be prepared by adding a metal source and a sulfur source together in a water bath or hydrothermal method, and the preparation method is simple. So that g-C3N4Compounding with ZIS, and using the obtained composite structure for high-efficiency photocatalytic H production2O2In the reaction of (2) to increase H2O2The yield was feasible.
Specifically, the inventor successfully synthesizes the g-C by self-assembly, water bath growth and high-temperature heat treatment3N4And a ZIS composite structure CN-ZIS. Synthesizing a hexagonal rod-shaped supermolecule precursor by self-assembly of melamine and solid phosphorous acid, growing a layer of ZIS nanosheet on the precursor in a water bath stirring mode, and finally, passing through high temperatureHeat treatment to polymerize supramolecular precursors to tubular C3N4(CN). The final CN-ZIS heterostructure is hexagonal tubular C3N4ZIS nano-sheets are grown on the surface of the substrate, and the unique hollow tubular structure can promote the absorption of visible light. In addition, the energy band structure matching between CN and ZIS can form type II heterojunction, thereby greatly promoting the separation of photo-generated charges.
The present invention will be described in detail with reference to the following embodiments.
Example 1
(1) Under the condition of stirring in a water bath at the temperature of 80 ℃, 1g of melamine is added into distilled water with the volume of 80 times, 1.2g of phosphorous acid is added after stirring for 30min, and stirring is continued for 60min to obtain a mixture.
(2) Transferring the mixture obtained in the step (1) into a reaction kettle, heating in an oven, and keeping at 180 ℃ for 10 hours; then, carrying out centrifugal operation on the obtained product, wherein the rotating speed is 4000r/min, and the time is 3min; and then putting the obtained product into a drying oven for drying at the temperature of 60 ℃ for 10 hours to obtain the precursor.
(3) 1g of the precursor obtained in step (2) was taken and added to 40mL of distilled water, and the pH was adjusted to about 2. Then, 0.2mmoL of indium chloride tetrahydrate and 0.1mmoL of zinc chloride are added, and stirred for 60min to obtain a mixed solution; adding 3.2mmoL thioacetamide into the mixed solution, and stirring for 30min; then transferring the solution into a water bath kettle to be stirred in a water bath way for 120min; and carrying out centrifugal operation on the obtained product and drying the product in a drying box at the temperature of 60 ℃ for 10 hours to obtain the precursor with the flaky sulfur indium zinc.
(4) And calcining the precursor with the flaky sulfur indium zinc in a tubular furnace at 500 ℃ for 2h to obtain the carbon nitride-sulfur indium zinc heterogeneous material.
FIG. 1 is a scanning electron microscope image of a precursor obtained by self-assembly of melamine and solid phosphorous acid, and as can be seen from FIG. 1, the prepared productThe precursor has a hexagonal rod structure. Photocatalytic H production of carbon nitride/InS heterogeneous material obtained in example 12O2The performance is shown in figure 5 with reference number 1.
Example 2
(1) Under the condition of stirring in a water bath at the temperature of 80 ℃, 1g of melamine is added into distilled water with the volume of 80 times, 1.2g of phosphorous acid is added after stirring for 30min, and stirring is continued for 60min to obtain a mixture.
(2) Transferring the mixture obtained in the step (1) into a reaction kettle, heating in an oven, and keeping at 180 ℃ for 10 hours; then, carrying out centrifugal operation on the obtained product, wherein the rotating speed is 4000r/min, and the time is 3min; and then putting the obtained product into a drying oven for drying at the temperature of 60 ℃ for 10 hours to obtain the precursor.
(3) 1g of the precursor obtained in step (2) was taken and added to 40mL of distilled water, and the pH was adjusted to about 2. Then, 0.4mmoL of indium chloride tetrahydrate and 0.2mmoL of zinc chloride are added, and stirred for 60min to obtain a mixed solution; adding 3.2mmoL thioacetamide into the mixed solution, and stirring for 30min; then transferring the solution into a water bath kettle to be stirred for 120min in a water bath way; and carrying out centrifugal operation on the obtained product and drying the product in a drying box at the temperature of 60 ℃ for 10 hours to obtain the precursor with the flaky sulfur indium zinc.
(4) And calcining the precursor with the flaky sulfur indium zinc in a tubular furnace at the calcining temperature of 500 ℃ for 2 hours to obtain the carbon nitride/sulfur indium zinc heterogeneous material.
Fig. 2 is a scanning electron microscope image of a precursor after growth of a layer of zinc indium sulfide thereon (i.e., a flaky zinc indium sulfide precursor), followed by calcination to obtain a carbon nitride/zinc indium sulfide heterogeneous material. Fig. 3 and 4 are a scanning electron microscope and a projection electron microscope of the carbon nitride/zinc indium sulfide heterogeneous material obtained in example 2, respectively, and it can be seen that zinc indium sulfide nanosheets uniformly grow on the carbon nitride tubes, which not only improves the corresponding ability of visible light, but also facilitates efficient separation and separation of photo-generated charges. The photocatalytic performance of the carbon nitride-sulfur indium zinc heterogeneous material obtained in the example 2 is shown as the reference numeral 2 in the figure 5, and can reach 2.77mmol g-1h-1。
Example 3
(1) Under the condition of stirring in a water bath at the temperature of 80 ℃, 1g of melamine is added into distilled water with the volume being 80 times that of the melamine, 1.2g of phosphorous acid is added after stirring for 30min, and stirring is continued for 60min to obtain a mixture.
(2) Transferring the mixture obtained in the step (1) into a reaction kettle, heating in an oven, and keeping at 180 ℃ for 10 hours; then, carrying out centrifugal operation on the obtained product, wherein the rotating speed is 4000r/min, and the time is 3min; and then putting the obtained product into a drying oven for drying at the temperature of 60 ℃ for 10 hours to obtain the precursor.
(3) 1g of the precursor obtained in step (2) was taken and added to 40mL of distilled water, and the pH was adjusted to about 2. Then, 0.6mmoL of indium chloride tetrahydrate and 0.3mmoL of zinc chloride are added, and stirred for 60min to obtain a mixed solution; adding 3.2mmoL thioacetamide into the mixed solution, and stirring for 30min; then transferring the solution into a water bath kettle to be stirred for 120min in a water bath way; and carrying out centrifugal operation on the obtained product and drying the product in a drying box at the temperature of 60 ℃ for 10 hours to obtain the precursor with the flaky sulfur indium zinc.
(4) And calcining the precursor with the flaky sulfur indium zinc in a tubular furnace at 500 ℃ for 2h to obtain the carbon nitride/sulfur indium zinc heterogeneous material.
Example 4
(1) Under the condition of stirring in a water bath at the temperature of 80 ℃, 1g of melamine is added into distilled water with the volume being 80 times that of the melamine, 1.2g of phosphorous acid is added after stirring for 30min, and stirring is continued for 60min to obtain a mixture.
(2) Transferring the mixture obtained in the step (1) into a reaction kettle, heating in an oven, and keeping at 180 ℃ for 10 hours; then, carrying out centrifugal operation on the obtained product, wherein the rotating speed is 4000r/min, and the time is 3min; and then putting the obtained product into a drying oven for drying at the temperature of 60 ℃ for 10 hours to obtain the precursor.
(3) 1g of the precursor obtained in step (2) was taken and added to 40mL of distilled water, and the pH was adjusted to about 2. Then, 0.8mmoL of indium chloride tetrahydrate and 0.4mmoL of zinc chloride are added, and stirred for 60min to obtain a mixed solution; adding 3.2mmoL thioacetamide into the mixed solution, and stirring for 30min; then transferring the solution into a water bath kettle to be stirred for 120min in a water bath way; and carrying out centrifugal operation on the obtained product and drying the product in a drying box at the temperature of 60 ℃ for 10 hours to obtain the precursor with the flaky sulfur indium zinc.
(4) And calcining the precursor with the flaky sulfur indium zinc in a tubular furnace at the calcining temperature of 500 ℃ for 2 hours to obtain the carbon nitride-sulfur indium zinc heterogeneous material.
FIG. 5, reference numeral 4, shows the photocatalytic H production of the carbon nitride-S-in-Zn heterostructure obtained in the present example2O2And (4) performance.
Example 5
(1) Under the condition of stirring in a water bath at 60 ℃, 1g of melamine is added into distilled water with the volume of 80 times, 1.2g of phosphorous acid is added after stirring for 30min, and stirring is continued for 60min to obtain a mixture.
(2) Transferring the mixture obtained in the step (1) into a reaction kettle, heating in an oven, and keeping at 180 ℃ for 10 hours; then, carrying out centrifugal operation on the obtained product, wherein the rotating speed is 4000r/min, and the time is 3min; and then putting the obtained product into a drying oven for drying at the temperature of 60 ℃ for 10 hours to obtain the precursor.
(3) 1g of the precursor obtained in step (2) was taken and added to 40mL of distilled water, and the pH was adjusted to around 2. Then, 0.4mmoL of indium chloride tetrahydrate and 0.2mmoL of zinc chloride are added, and stirred for 60min to obtain a mixed solution; adding 3.2mmoL thioacetamide into the mixed solution, and stirring for 30min; then transferring the solution into a water bath kettle to be stirred for 120min in a water bath way; and carrying out centrifugal operation on the obtained product and drying the product in a drying box at the temperature of 60 ℃ for 10 hours to obtain the precursor with the flaky sulfur indium zinc.
(4) And calcining the precursor with the flaky sulfur indium zinc in a tubular furnace at 500 ℃ for 2h to obtain the carbon nitride-sulfur indium zinc heterogeneous material.
Photocatalytic production of H from the obtained carbon nitride-sulfur indium zinc heterogeneous material2O2The properties were 0.94mmol g-1h-1。
Example 6
Embodiment 6 provides a method for preparing a carbon nitride-sulfur indium zinc heterostructure material, which specifically comprises the following steps:
(1) Under the condition of stirring in a water bath at 100 ℃, 1g of melamine is added into distilled water with the volume being 80 times that of the melamine, 1.2g of phosphorous acid is added after stirring for 30min, and stirring is continued for 60min to obtain a mixture.
(2) Transferring the mixture obtained in the step (1) into a reaction kettle, heating in an oven, and keeping at 180 ℃ for 10 hours; then, carrying out centrifugal operation on the obtained product, wherein the rotating speed is 4000r/min, and the time is 3min; and then putting the obtained product into a drying oven for drying at the temperature of 60 ℃ for 10 hours to obtain a precursor.
(3) 1g of the precursor obtained in step (2) was taken and added to 40mL of distilled water, and the pH was adjusted to about 2. Then, 0.4mmoL of indium chloride tetrahydrate and 0.2mmoL of zinc chloride are added, and stirred for 60min to obtain a mixed solution; adding 3.2mmoL thioacetamide into the mixed solution, and stirring for 30min; then transferring the solution into a water bath kettle to be stirred for 120min in a water bath way; and carrying out centrifugal operation on the obtained product and drying the product in a drying box at the temperature of 60 ℃ for 10 hours to obtain the precursor with the flaky sulfur indium zinc.
(4) And calcining the precursor with the flaky sulfur indium zinc in a tubular furnace at 500 ℃ for 2h to obtain the carbon nitride-sulfur indium zinc heterogeneous material.
Photocatalytic production of H from the obtained carbon nitride-sulfur indium zinc heterogeneous material2O2The properties were 1.07mmol g-1h-1。
Comparative example
ZIn2S4/g-C3N4Is a conventional process for producing H2O215mg of the carbon nitride/sulfur indium zinc heterogeneous material of example 2 and 15mg of the conventional ZIn were used as the photocatalyst, respectively2S4/g-C3N4In two photocatalytic reactors, the photocatalyst, 15mg, was dispersed in 50mL of an aqueous solution (containing 10vol% ethanol as the sacrificial electron donor) and O was used2Bubbling for 30 minutes. The photocatalytic suspension was irradiated from the top using a 300W Xe lamp equipped with an am1.5g filter as light source, and the bottom was passed through with water condensation and with constant stirring. H2O2The content of (b) is measured by a titanium potassium oxalate method. After 1h, quantitative suspensions were withdrawn from the two systems for testing. Example 2H as obtained at reference numeral 2 in FIG. 52O2Yield of (2.77 mmol g)-1h-1ZIn obtained as reference numeral 5 in FIG. 52S4/g-C3N4H of (A) to (B)2O2Yield of (5) was 0.86mmol g-1h-1. As can be seen, the photocatalytic H production of the carbon nitride-sulfur indium zinc heterogeneous material obtained in the example 22O2ZIn provided by performance versus ratio2S4/g-C3N4More preferably.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the present application, and that various changes in form and details may be made therein without departing from the spirit and scope of the present application in practice. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the scope or spirit of the present disclosure, and the scope of the present disclosure should be defined only by the appended claims.
Claims (10)
1. A preparation method of a carbon nitride-sulfur indium zinc heterogeneous material is characterized by comprising the steps of taking a precursor formed by self-assembly of melamine and phosphorous acid as a template, and growing a layer of flaky sulfur indium zinc on the precursor by a water bath stirring method; and polymerizing the precursor with the flaky sulfur indium zinc into tubular carbon nitride by a high-temperature calcination method to obtain the carbon nitride/sulfur indium zinc heterogeneous material.
2. The method for preparing a carbon nitride-sulfur indium zinc heterogeneous material according to claim 1, which comprises the following steps:
(1) Adding melamine into distilled water at the temperature of 60-100 ℃, stirring for 20-50 min, adding solid phosphorous acid, and continuously stirring for 40-80 min to obtain a mixture;
(2) Transferring the mixture into a reaction kettle for heating reaction, and then performing centrifugal operation and drying operation to obtain a precursor;
(3) Adding the precursor into distilled water, adjusting the pH value, adding indium salt and zinc salt, stirring for 60-180 min, adding a sulfur source, continuously stirring for 10-40 min, finally putting the reaction system into a water bath, heating in a water bath, stirring for 60-180 min, performing centrifugal operation, and collecting to obtain the precursor with the flaky sulfur indium zinc;
(4) And washing and drying the precursor on which the flaky sulfur indium zinc grows, and calcining the precursor in a tubular furnace to obtain the carbon nitride-sulfur indium zinc heterogeneous material.
3. The method for preparing the carbon nitride-sulfur indium zinc heterogeneous material according to the claim 2, wherein in the step (1), the mass ratio of the melamine to the solid phosphorous acid is 1.
4. The method for preparing the carbon nitride-sulfur indium zinc heterogeneous material as claimed in claim 2, wherein in the step (2), the temperature of the heating reaction is 160 ℃ to 200 ℃, and the holding time is 8h to 12h;
the rotating speed of the centrifugal operation is 3000 r/min-5000 r/min, and the time is 2 min-5 min;
the temperature of the drying operation is 40-80 ℃, and the time is 6-12 h.
5. The method for preparing a carbon nitride-sulfur indium zinc heterogeneous material according to claim 2, wherein in the step (3), the pH is adjusted to 1 to 3;
the mass ratio of the precursor to the indium salt is 1.059-0.23, the molar ratio of the indium salt to the zinc salt is 1-3;
the temperature of the water bath heating is 60-100 ℃.
6. The method for preparing a carbon nitride-sulfur indium zinc heterogeneous material according to claim 2 or 5, wherein in the step (3), the indium salt is one or more of indium bromide, indium nitrate and indium chloride;
the zinc salt is one or more of zinc acetate, zinc nitrate and zinc chloride;
the rotating speed of the centrifugal operation is 3000 r/min-5000 r/min, and the time is 2 min-5 min.
7. The method for preparing a carbon nitride-sulfur indium zinc heterogeneous material according to claim 4, wherein in the step (4), the drying conditions are as follows: the drying temperature is 40-80 ℃, and the drying time is 6-12 h.
8. A carbon nitride/sulfur indium zinc heterogeneous material, which is the carbon nitride-sulfur indium zinc heterogeneous material prepared by the preparation method of the carbon nitride/sulfur indium zinc heterogeneous material according to any one of claims 1 to 7.
9. The carbon nitride-sulfur indium zinc heterogeneous material according to claim 8, wherein the heterogeneous material is a tubular carbon nitride-sulfur indium zinc core-shell structure.
10. The carbon nitride/sulfur indium zinc heterogeneous material as claimed in claim 9 for photocatalytic H production2O2The use of (1).
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