CN112916035A - Fish scale tubular carbon nitride composite heterojunction photocatalyst and preparation method and application thereof - Google Patents
Fish scale tubular carbon nitride composite heterojunction photocatalyst and preparation method and application thereof Download PDFInfo
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- CN112916035A CN112916035A CN202110081203.8A CN202110081203A CN112916035A CN 112916035 A CN112916035 A CN 112916035A CN 202110081203 A CN202110081203 A CN 202110081203A CN 112916035 A CN112916035 A CN 112916035A
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- tubular carbon
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 301
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- 238000002360 preparation method Methods 0.000 title claims abstract description 37
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- PSCMQHVBLHHWTO-UHFFFAOYSA-K Indium trichloride Inorganic materials Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims abstract description 11
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
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- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- YMDCAYHEWFKCFR-UHFFFAOYSA-N 1-hydroxy-1-oxidopiperidin-1-ium Chemical compound O[N+]1([O-])CCCCC1 YMDCAYHEWFKCFR-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
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- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
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- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 239000002351 wastewater Substances 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
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- 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
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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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- 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
- C01B15/029—Preparation from hydrogen and oxygen
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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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a fish scale tubular carbon nitride composite heterojunction photocatalyst as well as a preparation method and application thereof, wherein the catalyst takes fish scale tubular carbon nitride as a framework, and the surface of the catalyst is modified with ZnI with the mass percentage content of less than or equal to 50 percentn2S4. The preparation method comprises the following steps: sequentially reacting ZnCl2、InCl3And adding thioacetamide into the suspension of the fish scale tubular carbon nitride and water, and carrying out hydrothermal reaction on the obtained precursor solution to obtain the catalyst. The fish scale tubular carbon nitride composite heterojunction photocatalyst has the advantages of strong light absorption capacity, low photoproduction electron-hole recombination rate, good photocatalytic performance, good stability and the like, is a novel carbon nitride photocatalytic material, can be widely used for removing organic pollutants through photocatalysis and preparing H product2O2The preparation method has the advantages of simple process, easily controlled conditions, low cost and the like, is suitable for large-scale industrial production, and is beneficial to industrial application.
Description
Technical Field
The invention relates to a carbon nitride composite heterojunction photocatalyst as well as a preparation method and application thereof, in particular to a fish scale tubular carbon nitride composite heterojunction photocatalyst as well as a preparation method and application thereof2O2The use of (1).
Background
With the rapid development of economy, environmental and energy problems have become a problem which needs to be solved urgently today. Antibiotic drugs are widely used, the antibiotic drugs are often detected in natural water, sewage, soil and other environmental media due to overuse and incomplete metabolism, and the unmetabolized antibiotic drugs probably influence the development of biological cells and are ecologicallySystemic circulation and promotion of the propagation of drug-resistant pathogenic bacteria, which adversely affect the ecological environment and human health. At present, common methods for removing antibiotics in water environments at home and abroad comprise a biological method, a physicochemical method, an electrochemical method and a filtration method. Although the biological method is low in cost, the required time is long, and the removal effect is interfered by multiple factors. The electrochemical method has high unit treatment cost for low-concentration pollutants, and is difficult to use on a large scale. Filtration simply transfers contaminants from one phase to the other and does not mineralize them into carbon dioxide and water. Photocatalytic degradation in physicochemical methods can be seen as an effective and environmentally friendly method. In terms of energy, hydrogen peroxide (H)2O2) Has attracted considerable attention not only because it can be used as a power source for fuel cells, but also because it is a clean general oxidant for disinfection and environmental remediation. However, the traditional preparation techniques of hydrogen peroxide, such as anthraquinone method, electrocatalytic oxygen reduction method, etc., have the defects of complex process, high cost, etc., and limit the practical application value thereof. Semiconductor photocatalytic technology using clean solar energy is considered as an effective strategy to address the current environmental and energy crisis. However, in the previous studies, the following problems still remain in the photocatalyst used for photocatalytic degradation: the method has the advantages of low light utilization efficiency, fast photoproduction electron-hole recombination, poor photocatalytic performance, poor stability and the like, and greatly limits the wide application of photocatalytic degradation due to a large number of defects of the photocatalyst.
A large number of materials have been found to have photocatalytic properties to date, which mainly include metal-based photocatalytic materials and non-metal-based photocatalytic materials. In recent years, carbon nitride-based photocatalytic materials, in which carbon nitride material (g-C) is widely used for research in the field of photocatalysts because of its low cost and good photoresponse ability3N4) Is a typical carbon nitride-based photocatalytic material (g-C)3N4Energy gap of about 2.7eV), however, g-C3N4The g-C is greatly limited by the problems of small specific surface area, easy recombination of photoproduction electrons and holes, weak visible light absorption capacity, weak photocatalytic performance and the like3N4The use of (1). To improve g-C3N4Of (2) photocatalytic properties, typically in the range of g-C3N4The photocatalyst is compounded with other materials to form a heterojunction photocatalytic system, and the heterojunction photocatalytic system can obviously improve the absorption range of the photocatalytic material on a spectrum and accelerate the separation speed of photoproduction electrons and holes, so that the photocatalytic performance of the photocatalyst is improved. However, the existing carbon nitride-based composite heterojunction photocatalytic material still has the defects of weak light absorption capacity, slow photoproduction electron-hole separation rate, poor photocatalytic activity and the like, is difficult to effectively degrade organic pollutants in water, and is also not beneficial to improving the yield of hydrogen peroxide, so that the wide application of the carbon nitride-based composite heterojunction photocatalytic material in the field of photocatalysis is limited. In addition, the surface of the existing tubular carbon nitride is planar and smooth, which is not beneficial to the stable loading of other heterojunction materials, so that the tubular carbon nitride-based heterojunction material with stable performance is difficult to construct, and meanwhile, the existing tubular carbon nitride also has the defects of uneven structure, unstable structure, small specific surface area, weak light absorption capacity, easy recombination of photo-generated electrons and holes, poor photocatalytic performance and the like, and the existence of the defects greatly limits the wide application of the tubular carbon nitride as a carrier material in constructing the heterojunction composite material, and is difficult to meet the requirements in the field of photocatalysis. In addition, no relevant report on the preparation of the fish scale tubular carbon nitride is found so far.
Therefore, the fish scale tubular carbon nitride which has the advantages of large specific surface area, strong visible light absorption capacity, high photoproduction electron-hole separation efficiency, high catalytic activity and good structural stability, and the matched preparation method which has the advantages of simple process, convenient operation, mild reaction conditions, no need of complex equipment and low cost are obtained, and the method has very important significance for preparing the high-performance fish scale tubular carbon nitride composite heterojunction photocatalyst and improving the application range of the fish scale tubular carbon nitride composite heterojunction photocatalyst in the field of photocatalysis.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide the fish scale tubular carbon nitride composite heterojunction photocatalyst which has strong light absorption capacity, low photoproduction electron-hole recombination rate, good photocatalytic performance and good stability, and the preparation method and the application thereof.
In order to solve the technical problems, the invention adopts the technical scheme that:
the fish scale tubular carbon nitride composite heterojunction photocatalyst takes fish scale tubular carbon nitride as a framework, and the surface of the fish scale tubular carbon nitride is modified with ZnIn2S4(ii) a ZnIn in the fish scale tubular carbon nitride composite heterojunction photocatalyst2S4The mass percentage content of the component (A) is less than or equal to 50 percent.
In the fish scale tubular carbon nitride composite heterojunction photocatalyst, the ZnIn in the fish scale tubular carbon nitride composite heterojunction photocatalyst is further improved2S4The mass percentage of the component (A) is 2-50%.
In the fish scale tubular carbon nitride composite heterojunction photocatalyst, the fish scale tubular carbon nitride is further improved to be of a tubular structure, and the surface of the fish scale tubular carbon nitride is formed by fish scales; the ZnIn2S4Is in a flower-shaped spherical structure.
As a general technical concept, the invention also provides a preparation method of the fish scale tubular carbon nitride composite heterojunction photocatalyst, which comprises the following steps:
(1) sequentially reacting ZnCl2、InCl3Adding thioacetamide into a suspension of fish scale tubular carbon nitride and water, and stirring to obtain a precursor solution;
(2) and (2) carrying out hydrothermal reaction on the precursor solution obtained in the step (1) to obtain the fish scale tubular carbon nitride composite heterojunction photocatalyst.
The preparation method of the fish scale tubular carbon nitride composite heterojunction photocatalyst is further improved, and comprises the following steps:
s1, respectively dissolving melamine and trithiocyanuric acid in an organic solvent to obtain a melamine solution and a trithiocyanuric acid solution;
s2, mixing the melamine solution and the trithiocyanuric acid solution obtained in the step S1, and stirring to obtain a mixed solution of melamine and trithiocyanuric acid;
s3, adding water into the mixed solution of melamine and trithiocyanuric acid obtained in the step S2, filtering and drying to obtain a tubular mixture of melamine and trithiocyanuric acid;
s4, calcining the mixture of the tubular melamine and the cyanuric acid obtained in the step S2 to obtain the fish scale tubular carbon nitride.
In the preparation method of the fish scale tubular carbon nitride composite heterojunction photocatalyst, the ratio of the melamine to the organic solvent is 1 g: 30 mL-50 mL in the step S1; the ratio of the trithiocyanuric acid to the organic solvent is 1 g: 30 mL-50 mL; the organic solvent is at least one of ethanol, N-dimethylformamide and dimethyl sulfoxide.
In the step S2, the molar ratio of melamine to trithiocyanuric acid in the mixed solution of melamine and trithiocyanuric acid is 0.5-1.5: 1; the concentration of melamine in the mixed solution of melamine and trithiocyanuric acid is 0.05-0.15M; the stirring is carried out at the temperature of 20-80 ℃; the rotating speed of the stirring is 600 rpm; the stirring time is 1-4 h.
In the preparation method of the fish scale tubular carbon nitride composite heterojunction photocatalyst, the volume ratio of the mixed solution of melamine and trithiocyanuric acid to water is 6-10: 5-20 in step S3; the drying temperature is 70-80 ℃.
In the above preparation method of the fish scale tubular carbon nitride composite heterojunction photocatalyst, the calcination is performed in a nitrogen atmosphere or an argon atmosphere in step S4; the heating rate in the calcining process is 2.3 ℃/min; the calcining temperature is 450-550 ℃; the calcining time is 2-4 h.
The preparation method of the fish scale tubular carbon nitride composite heterojunction photocatalyst is further improvedIn the step (1), the precursor solution contains fish scale tubular carbon nitride and ZnCl2、InCl3The mass ratio of the thioacetamide to the thioacetamide is 423: 4.14: 13.12: 6-423: 103.5: 328: 150; the ratio of the fish scale tubular carbon nitride to the water in the suspension of the fish scale tubular carbon nitride and the water is 0.47 g: 80 mL; the stirring time is 2 h.
In the preparation method of the fish scale tubular carbon nitride composite heterojunction photocatalyst, the hydrothermal reaction is carried out in a high-pressure reaction kettle in the step (2); the temperature of the hydrothermal reaction is 180 ℃; the time of the hydrothermal reaction is 12 h.
As a general technical concept, the invention also provides the fish scale tubular carbon nitride composite heterojunction photocatalyst prepared by the preparation method or the fish scale tubular carbon nitride composite heterojunction photocatalyst for removing organic pollutants in water or preparing H2O2The use of (1).
In the above application, further improved, when the fish scale tubular carbon nitride is used for removing antibiotics in a water body, the method comprises the following steps: mixing the fish scale tubular carbon nitride composite heterojunction photocatalyst with water containing organic pollutants, stirring, and carrying out photocatalytic reaction under the condition of illumination to finish the removal of the organic pollutants in the water.
The application is further improved, when the fish scale tubular carbon nitride is used for removing antibiotics in a water body, the ratio of the fish scale tubular carbon nitride composite heterojunction photocatalyst to the water body containing organic pollutants is 0.5-1 g: 1L; the organic pollutants in the water body containing the organic pollutants are antibiotics and/or dyes; the antibiotic is tetracycline hydrochloride; the initial concentration of the organic pollutants in the water body containing the organic pollutants is less than or equal to 20 mg/L; the stirring is carried out under dark conditions; the rotating speed of the stirring is 500-800 rpm; the stirring time is 30 min; the light source adopted in the photocatalytic reaction is a xenon lamp, and the optical power is 45-50W; the photocatalytic reaction is carried out under the stirring condition with the rotating speed of 500 rpm-800 rpm; the temperature of the photocatalytic reaction is 25-35 ℃; the time of the photocatalytic reaction is 30-120 min.
In the application, the improved tubular carbon nitride of the fish scale is used for preparing H2O2The method comprises the following steps: mixing the fish scale tubular carbon nitride composite heterojunction photocatalyst with water, introducing oxygen, and carrying out photocatalytic reaction under the condition of illumination to obtain H2O2。
In the application, the improved tubular carbon nitride of the fish scale is used for preparing H2O2When in use, the ratio of the fish scale tubular carbon nitride composite heterojunction photocatalyst to water is 0.5-1 g: 1L; introducing oxygen under dark conditions; the introducing time of the oxygen is 30 min; the light source adopted in the photocatalytic reaction is a xenon lamp, and the optical power is 45-50W; the photocatalytic reaction is carried out under the stirring condition with the rotating speed of 500 rpm-800 rpm; the temperature of the photocatalytic reaction is 25-35 ℃; the time of the photocatalytic reaction is 30-120 min; a sacrificial agent is also added into the photocatalytic reaction system; the volume ratio of the sacrificial agent to the water is 1: 10; the sacrificial agent is ethanol and/or isopropanol.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a fish scale tubular carbon nitride composite heterojunction photocatalyst, which takes fish scale tubular carbon nitride as a framework, and ZnIn is modified on the surface of the fish scale tubular carbon nitride2S4In which ZnIn2S4The mass percentage content of the component (A) is less than or equal to 50 percent. The fish scale tubular carbon nitride adopted in the invention has the advantages of large specific surface area, strong visible light absorption capacity, high photoproduction electron-hole separation efficiency, high catalytic activity, good structural stability and the like, and can more stably separate ZnIn by using the fish scale tubular carbon nitride as a framework material2S4Loading on the surface of fish scale tubular carbon nitride to obtain a composite material with stable structure, wherein on one hand, ZnIn is added2S4Modifying the surface of the fish scale tubular carbon nitride to ensure that the carbon nitride and ZnIn are mixed2S4A heterojunction is formed between the two layers, so that the transfer of electrons and holes can be accelerated, the recombination of the electrons and the holes can be inhibited, and the photocatalytic performance can be improvedOn the other hand, the fish scale tubular carbon nitride has better conductivity and can transfer electrons more quickly, so that the separation efficiency of electrons and holes is higher, and better photocatalytic activity is more favorably obtained. More importantly, by optimizing ZnIn2S4Can reduce the excessive ZnIn2S4The composite heterojunction photocatalyst can shield the fish scale tubular carbon nitride, so that the composite heterojunction photocatalyst has excellent photocatalytic performance. The fish scale tubular carbon nitride composite heterojunction photocatalyst has the advantages of strong light absorption capacity, low photoproduction electron-hole recombination rate, good photocatalytic performance, good stability and the like, is a novel carbon nitride photocatalytic material, and can be widely used for removing organic pollutants (such as antibiotics and dyes) in the environment and preparing H through photocatalysis2O2Has good application prospect.
(2) In the fish scale tubular carbon nitride composite heterojunction photocatalyst, ZnIn is further optimized2S4The weight percentage of the composite photocatalyst is 2-50%, so that the fish scale tubular carbon nitride composite heterojunction photocatalyst has better photocatalytic performance, because the composite proportion has important influence on the performance of the photocatalyst. E.g. when ZnIn2S4When the mass percentage of (B) is higher than 50%, ZnIn is excessively doped2S4The material has strong adsorption performance, and the photocatalytic performance is inhibited, so that the photocatalytic performance of the material is reduced; when ZnIn is present2S4When the mass percentage of (B) is less than 2%, less ZnIn is contained2S4The photocatalysis performance of the composite heterojunction is not promoted to be better exerted, so that the photocatalysis performance of the composite material is reduced. Thus, carbon nitride and ZnIn2S4The optimum photocatalytic performance can be exerted only when the compound proportion is proper, and particularly, the ZnIn in the invention2S4The weight percentage of the titanium nitride is 2-50 percent, the weight percentage of the carbon nitride is 50-98 percent, and the synergistic effect between the two materials can be further promoted, so that the fish scale tubular carbon nitride composite heterojunction photocatalyst can obtain better effectPhotocatalytic performance.
(4) The invention provides a preparation method of a fish scale tubular carbon nitride composite heterojunction photocatalyst, which uses fish scale tubular carbon nitride and ZnIn2、InCl3And thioacetamide as raw materials, sequentially adding ZnCl2、InCl3Adding thioacetamide into the suspension of fish scale tubular carbon nitride and water to prepare a precursor solution, and further generating ZnIn through a hydrothermal reaction2S4And the compound photocatalyst grows on the surface of the fish scale tubular carbon nitride in situ, so that the fish scale tubular carbon nitride compound heterojunction photocatalyst with strong light absorption capacity, low photoproduction electron-hole recombination rate, good photocatalytic performance and good stability is obtained. In the present invention, ZnCl is successively introduced2、InCl3The thioacetamide is added into the suspension of the fish scale tubular carbon nitride and water, and the advantages are as follows: zn2+Can firstly form strong cation-pi interaction with benzene ring of carbon nitride to lead Zn to be2+Adsorbed on the surface of carbon nitride, thereby enabling the subsequent addition of InCl3ZnIn formed after reaction with thioacetamide2S4The catalyst can grow on the surface of the pipe wall of the fish scale tubular carbon nitride more stably in situ, and is more beneficial to obtaining the fish scale tubular carbon nitride composite heterojunction photocatalyst with good catalytic performance and good stability. The preparation method of the fish scale tubular carbon nitride composite heterojunction photocatalyst has the advantages of simple process, easily controlled conditions, low cost and the like, is suitable for large-scale industrial production, and is beneficial to industrial application.
(5) In the preparation method of the fish scale tubular carbon nitride composite heterojunction photocatalyst, melamine and trithiocyanuric acid are used as raw materials, are fully dissolved in an organic solvent, then the solution of the melamine and the trithiocyanuric acid is mixed to form a tubular self-assembled aggregate through self-assembly, the melamine and the trithiocyanuric acid are fully dissolved in the organic solvent, so that the self-assembly between the melamine and the trithiocyanuric acid is more thorough and uniform, the tubular self-assembled aggregate cannot be separated out by using water, other solvents cannot realize the separation, and the tubular self-assembled aggregate is calcinedUniform, therefore, the melamine melted in the calcination temperature rise process is weak in force field within a certain range due to edge effect and easy to move, so that fish scale structure is formed, and simultaneously, the melamine and trithiocyanuric acid are decomposed along with the temperature rise of the calcination temperature, so that a large amount of gas such as H is generated2S and NH3Resulting in pore structure and defects on the surface of the self-assembled aggregate, thereby preparing the flake tubular carbon nitride. Compared with the conventional tubular carbon nitride, the fish scale tubular carbon nitride prepared by the method has the following advantages: the surfaces of the fish scale tubular carbon nitride consist of fish scales, have rough surface appearance and rich pore structures, have a large number of structural defects, can effectively improve the band gap structure, and are beneficial to greatly improving the photocatalytic performance; the fish scale tubular carbon nitride has stronger visible light absorption capacity, can improve an energy band structure, better protects a crystal region of the carbon nitride, and ensures excellent photoelectrochemical performance, so that the separation efficiency of photoproduction electrons and holes can be accelerated, the recombination of the photoproduction electrons and the holes is reduced, and the fish scale tubular carbon nitride has better photocatalytic activity; the fish scale tubular carbon nitride has a more stable structure, is not easy to break, and is favorable for directional transfer and separation of operation electrons, thereby being more favorable for improving the photocatalytic performance. The fish scale tubular carbon nitride prepared by the invention has the advantages of large specific surface area, strong visible light absorption capacity, high photoproduction electron-hole separation efficiency, high catalytic activity, good structural stability and the like, can be directly applied to the field of photocatalysis as a catalyst material, can also be used as a carrier of other materials for constructing a composite heterojunction material with stable structure and good photocatalytic performance, and is a novel carrier material with excellent photocatalytic activity. Meanwhile, the preparation method of the fish scale tubular carbon nitride has the advantages of simple process, convenient operation, mild reaction conditions, no need of complex equipment, low cost and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
(6) The invention provides an application of a fish scale tubular carbon nitride composite heterojunction photocatalyst in removing organic pollutants in a water body, wherein the fish scale tubular carbon nitride composite heterojunction photocatalyst and organic pollutants are mixedThe organic pollutants in the water body can be effectively removed by mixing the organic pollutants with the water body to carry out a photocatalytic reaction. According to the invention, the fish scale tubular carbon nitride composite heterojunction photocatalyst is used for photocatalytic degradation of organic pollutants, and accords with a heterojunction degradation mechanism, and the method specifically comprises the following steps: under the condition of illumination, electrons on the conduction band of the fish scale tubular carbon nitride are transferred to ZnIn2S4Generating holes, thereby making ZnIn2S4The conduction band of (1) accumulates a large amount of electrons and ZnIn2S4The valence band has more and more holes, so the reducibility of the valence band is stronger and the holes are accumulated in ZnIn2S4The conduction band has more and more electrons, so that the oxidation property of the conduction band is stronger and the strong oxidation reduction property can convert oxygen into superoxide radical (O) with strong oxidation property2 -) The final organic contaminant is in the presence of O having strong oxidizing property2 -And is degraded into carbon dioxide and water by the action of the reductive cavity. The method for removing the organic pollutants in the water body by using the fish scale tubular carbon nitride composite heterojunction photocatalyst can be used for carrying out photocatalytic degradation on the organic pollutants by using the fish scale tubular carbon nitride composite heterojunction photocatalyst, can be used for rapidly and efficiently degrading various types of organic pollutants (such as antibiotics and dyes) in the water body, has the advantages of simple process, low treatment cost, high treatment efficiency, good removal effect, high safety, no secondary pollution and the like, particularly can realize the efficient removal of the antibiotics in the water body, and has good practical application prospect.
(7) The invention provides a fish scale tubular carbon nitride composite heterojunction photocatalyst in preparation of H2O2The application of the method comprises the steps of mixing the fish scale tubular carbon nitride composite heterojunction photocatalyst with water, and introducing oxygen to carry out photocatalytic reaction to obtain H2O2. In the invention, the fish scale tubular carbon nitride composite heterojunction photocatalyst is used for preparing H through photocatalysis2O2The method conforms to a heterojunction degradation mechanism and specifically comprises the following steps: under the illumination condition, due to the existence of a heterojunction interface between semiconductors, electrons on a conduction band of the fish scale tubular carbon nitride are transferred to ZnIn2S4Generating holes, thereby making ZnIn2S4The conduction band of (1) accumulates a large amount of electrons and ZnIn2S4The valence band has more and more holes, so the reducibility of the valence band is stronger and the holes are accumulated in ZnIn2S4The conduction band has more and more electrons, so that the oxidation property of the conduction band is stronger and the strong oxidation reduction property can convert oxygen into superoxide radical (O) with strong oxidation property2 -) While being O2 -Can also convert H into2Oxidation of O to H2O2Therefore, the fish scale tubular carbon nitride composite heterojunction photocatalyst can be used for quickly and efficiently preparing H2O2. The invention utilizes the fish scale tubular carbon nitride composite heterojunction photocatalyst to prepare H2O2The method comprises the step of carrying out photocatalytic oxidation on water by utilizing a fish scale tubular carbon nitride composite heterojunction photocatalyst to prepare H2O2Has the advantages of simple process, low treatment cost, high treatment efficiency, high safety, no secondary pollution and the like, and simultaneously produces a large amount of H2O2And can also promote the degradation of pollutants and enhance the antibacterial capacity of the water body.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 shows a flake tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) prepared in example 1 of the present invention2S4/FTCNso) Fish scale tubular carbon nitride (FTCN)so) And ZnIn prepared in comparative example 12S4SEM image of (d).
FIG. 2 shows a flake tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) prepared in example 1 of the present invention2S4/FTCNso) Fish scale tubular carbon nitride (FTCN)so) A TEM image of (a).
FIG. 3 is a view showing a shape of a fish scale tube obtained in example 1 of the present inventionCarbon nitride composite heterojunction photocatalyst (2% ZnIn)2S4/FTCNso、5％ZnIn2S4/FTCNso、10％ZnIn2S4/FTCNso、50％ZnIn2S4/FTCNso) Fish scale tubular carbon nitride (FTCN)so) ZnIn prepared in comparative example 12S4Tubular Carbon Nitride (TCN) prepared in comparative example 2iso) And raw carbon nitride (g-C)3N4) XRD pattern of (a).
FIG. 4 shows a flake tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) prepared in example 1 of the present invention2S4/FTCNso) Fish scale tubular carbon nitride (FTCN)so) ZnIn prepared in comparative example 12S4And raw carbon nitride (g-C)3N4) N of (A)2Adsorption-removal of attached figure.
FIG. 5 shows a fish scale tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) prepared in example 1 of the present invention2S4/FTCNso) Fish scale tubular carbon nitride (FTCN)so) ZnIn prepared in comparative example 12S4And raw carbon nitride (g-C)3N4) XPS spectra of (A).
FIG. 6 shows a fish scale tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) prepared in inventive example 1 and prepared in inventive example 12S4/FTCNso) Fish scale tubular carbon nitride (FTCN)so) ZnIn prepared in comparative example 12S4Tubular Carbon Nitride (TCN) prepared in comparative example 2iso) And raw carbon nitride (g-C)3N4) Ultraviolet-visible diffuse reflectance spectrum of (a).
FIG. 7 shows a flake tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) prepared in example 1 of the present invention2S4/FTCNso) Fish scale tubular carbon nitride (FTCN)so) ZnIn prepared in comparative example 12S4Tubular Carbon Nitride (TCN) prepared in comparative example 2iso) And raw carbon nitride (g-C)3N4) Electrochemical performance diagram of (1).
FIG. 8 shows a flake tubular carbon nitride composite heterojunction photocatalyst (2% ZnIn) in example 2 of the present invention2S4/FTCNso、5％ZnIn2S4/FTCNso、10％ZnIn2S4/FTCNso、50％ZnIn2S4/FTCNso) Fish scale tubular carbon nitride (FTCN)so)、ZnIn2S4Tubular Carbon Nitride (TCN)iso) And raw carbon nitride (g-C)3N4) The degradation effect of the tetracycline hydrochloride is shown.
FIG. 9 shows a fish scale tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) in example 2 of the present invention2S4/FTCNso) The degradation effect of the tetracycline hydrochloride solution with different concentrations is shown.
FIG. 10 shows a fish scale tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) in example 2 of the present invention2S4/FTCNso) The degradation effect of the tetracycline hydrochloride solution under different electrolyte conditions is shown.
FIG. 11 shows a flake tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) in example 2 of the present invention2S4/FTCNso) The degradation effect of the tetracycline hydrochloride solution with different pH values is shown.
FIG. 12 shows a tubular carbon nitride composite heterojunction photocatalyst containing fish scales (5% ZnIn) in example 2 of the present invention2S4/FTCNso) Fish scale tubular carbon nitride (FTCN)so)、ZnIn2S4Tubular Carbon Nitride (TCN)iso) And raw carbon nitride (g-C)3N4) Zeta potential maps of tetracycline hydrochloride solutions of different pH values.
FIG. 13 shows a fish scale tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) in example 2 of the present invention2S4/FTCNso) The degradation effect of the tetracycline hydrochloride solution with different pH values under different capture agent conditions is shown.
FIG. 14 shows a fish scale tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) in example 2 of the present invention2S4/FTCNso) Active ingredientESR graph of (d).
Fig. 15 is a graph showing the mineralization effect of the fish scale tubular carbon nitride composite heterojunction photocatalyst on tetracycline hydrochloride in example 3 of the present invention.
Fig. 16 is a graph of the degradation effect of the flake tubular carbon nitride composite heterojunction photocatalyst of the invention in example 3 corresponding to repeated treatment of tetracycline hydrochloride solution.
FIG. 17 shows a flake tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) in example 4 of the present invention2S4/FTCNso) Fish scale tubular carbon nitride (FTCN)so)、ZnIn2S4Product of (H)2O2And (5) effect diagrams.
FIG. 18 shows the repeated preparation of H by using the flake tubular carbon nitride composite heterojunction photocatalyst in example 5 of the invention2O2The effect diagram of (1).
FIG. 19 is a degradation mechanism diagram of the flake tubular carbon nitride composite heterojunction photocatalyst of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The starting materials and equipment used in the following examples are commercially available. In the examples of the present invention, unless otherwise specified, the adopted process is a conventional process, the adopted equipment is conventional equipment, and the obtained data are average values of three or more repeated experiments.
Example 1
A fish scale tubular carbon nitride composite heterojunction photocatalyst takes fish scale tubular carbon nitride as a framework, and ZnIn is modified on the surface of the fish scale tubular carbon nitride2S4In which ZnIn2S4The mass percentage of (B) is 2%.
In the embodiment, the fish scale tubular carbon nitride is of a tubular structure, and the surface of the fish scale tubular carbon nitride is composed of the fish scales; ZnIn2S4Is in a flower-shaped spherical structure.
A preparation method of the flake tubular carbon nitride composite heterojunction photocatalyst in the embodiment includes the following steps:
(1) 1.08g of melamine and 1.41g of trithiocyanuric acid were added to 50mL of dimethyl sulfoxide, respectively, to obtain a melamine solution and a trithiocyanuric acid solution.
(2) And (2) mixing the melamine solution and the trithiocyanuric acid solution obtained in the step (1), and magnetically stirring at 600rpm for 4h at the temperature of 30 ℃ to obtain a yellow mixed solution of melamine and trithiocyanuric acid.
(3) And (3) adding 100mL of water into 100mL of the mixed solution of the yellow melamine and the trithiocyanuric acid obtained in the step (2), separating out a yellow precipitate, filtering, drying the obtained precipitate at 80 ℃, and grinding to obtain a tubular melamine and trithiocyanuric acid mixture.
(4) Placing 1.25g of the tubular mixture of melamine and trithiocyanuric acid obtained in the step (3) in a tubular furnace, heating to 550 ℃ at a heating rate of 2.3 ℃/min in a nitrogen atmosphere, and maintaining for 4h to obtain the fish scale tubular carbon nitride, which is marked as FTCNso。
(5) 0.47g of the FTCN obtained in the step (4)soThe mixture was placed in an inner liner of an autoclave containing 80mL of water, and 6.4mg of ZnIn was sequentially added every 5 minutes2、20.8mg InCl3And 15mg of thioacetamide, stirring for 2h, putting the lining filled with the precursor solution into an autoclave, placing the autoclave in an oven at 180 ℃ for 12h, cooling, filtering, drying and grinding to obtain the fish scale tubular carbon nitride composite heterojunction photocatalyst (ZnIn)2S4/FTCNso) 2% ZnIn2S4/FTCNso。
In this example, ZnIn was also prepared2S4The content of the fish scale tubular carbon nitride composite heterojunction photocatalyst is 5 percent of ZnIn2S4/FTCNso、10％ZnIn2S4/FTCNso、50％ZnIn2S4/FTCNso。
Comparative example 1
ZnIn2S4The preparation method comprises the following steps:
80mL of water was addedAdding 6.4mg of ZnIn into the inner lining of the autoclave in turn every 5 minutes2、20.8mg InCl3And 15mg thioacetamide, stirring for 2h, putting the lining filled with the precursor solution into an autoclave, placing the autoclave in an oven at 180 ℃ for 12h, cooling, filtering, drying and grinding to obtain ZnIn2S4。
Comparative example 2
Tubular Carbon Nitride (TCN)iso) The preparation method comprises the following steps:
(1) adding 1.01g of melamine and 1.41g of trithiocyanuric acid into 80mL of 50% ethanol solution, mixing, carrying out self-assembly under stirring, then keeping at 100 ℃ for 6h for hydrothermal reaction, filtering and drying after the reaction to obtain the tubular melamine/trithiocyanuric acid compound.
(2) Placing 1.25g of the tubular mixture of melamine and trithiocyanuric acid obtained in step (1) in a tubular furnace, heating to 550 ℃ at a heating rate of 2.3 ℃/min under nitrogen atmosphere, and maintaining for 4h to obtain tubular carbon nitride, which is marked as TCNiso。
FIG. 1 shows a flake tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) prepared in example 1 of the present invention2S4/FTCNso) Fish scale tubular carbon nitride (FTCN)so) And ZnIn prepared in comparative example 12S4SEM image of (d). In FIG. 1, (1-1) and (1-2) are FTCNso(1-3) is ZnIn2S4(1-4) 5% ZnIn2S4/FTCNso. As shown in FIG. 1, the fish scale is made of tubular carbon nitride (FTCN)so) The surface of (2) is very rough, a large number of nano pores exist on the surface, the existence of a large number of pores causes the fish scale tubular carbon nitride to have a large number of structural defects, and meanwhile, the fish scale tubular carbon nitride (FTCN) can be obviously seenso) The fish scale is of a tubular structure, the surface of the fish scale is composed of fish scales, and the size of the fish scales is 100 nm; ZnIn2S4Has a spherical flower-shaped structure and abundant folds; fish scale tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) obtained after in-situ growth and compounding2S4/FTCNso) Reserves FTCNsoAnd due to ZnIn2S4Some surface changes occur. In conclusion, the invention successfully constructs the fish scale tubular carbon nitride composite heterojunction photocatalyst with rich structural defects.
FIG. 2 shows a flake tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) prepared in example 1 of the present invention2S4/FTCNso) Fish scale tubular carbon nitride (FTCN)so) A TEM image of (a). In FIG. 1, (2-1) is FTCNso(2-2) 5% ZnIn2S4/FTCNso. As can be seen from FIG. 2, the tubular carbon nitride of fish scales is modified with ZnIn on the surface2S4This shows that after the compounding, the surface of the fish scale tubular carbon nitride is covered by a layer of substance, and it can be seen that the invention has successfully constructed the fish scale tubular carbon nitride compound heterojunction photocatalyst with rich structural defects, and the result is consistent with the result in SEM.
FIG. 3 shows a flake tubular carbon nitride composite heterojunction photocatalyst (2% ZnIn) prepared in example 1 of the present invention2S4/FTCNso、5％ZnIn2S4/FTCNso、10％ZnIn2S4/FTCNso、50％ZnIn2S4/FTCNso) Fish scale tubular carbon nitride (FTCN)so) ZnIn prepared in comparative example 12S4Tubular Carbon Nitride (TCN) prepared in comparative example 2iso) And raw carbon nitride (g-C)3N4) XRD pattern of (a). As can be seen from fig. 3, all samples have a total of four distinct diffraction peaks, specifically, the peak at 13.2 ° (100) corresponds to the in-plane structural stacking of the triazine units, while the other peak at 27.4 ° (002) corresponds to the interlayer stacking of the aromatic units. It is worth emphasizing that the completely dissolved self-assembled prepared FTCNsoRetains g-C3N4Crystal structure of (a), and insufficiently dissolved self-assembled prepared TCNisoDue to the fact that melamine and trithiocyanuric acid are sufficiently dissolved in an organic solvent in the preparation process of the present invention, and thus, one of melamine and trithiocyanuric acid is seriously damagedThe self-assembly between the two is more thorough and uniform. More importantly, fish scale tubular carbon nitride (FTCN)so) The ordered structure inside is beneficial to enhancing the photocatalytic activity. In addition, XRD spectrogram of fish scale tubular carbon nitride composite heterojunction photocatalyst follows ZnIn2S4Increase in content, in one aspect, g-C3N4The diffraction peaks (13.2 °, 27.4 °) of (b) gradually become weaker and disappear. On the other hand, diffraction peaks at 21.6 ° (006), 27.7 ° (102) and 47.2 ° (110) gradually increased, and thus the XRD results also indicate that the flake tubular carbon nitride composite heterojunction photocatalyst of the present invention was successfully synthesized.
FIG. 4 shows a flake tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) prepared in example 1 of the present invention2S4/FTCNso) Fish scale tubular carbon nitride (FTCN)so) ZnIn prepared in comparative example 12S4And raw carbon nitride (g-C)3N4) N of (A)2Adsorption-removal of attached figure. As can be seen in fig. 4, all samples are representative type III isotherms, indicating that all samples have a mesoporous structure. Then, the pore size distribution and the specific surface area were analyzed by BJH adsorption and BET methods, respectively, and the results showed that g-C3N4And ZnIn2S4Few mesopores, and FTCNsoAnd 5% ZnIn2S4/FTCNsoWith a large number of mesopores of about 30 nm. Furthermore, FTCNsoRatio g-C3N4And ZnIn2S4Has a larger specific surface area, which is associated with a rich population of pores. Due to the presence of porous FTCNsoThis also resulted in 5% ZnIn2S4/FTCNsoThe photocatalyst has large specific surface area, abundant pore structures and larger specific surface area, can provide more catalytic active sites, can promote the adsorption of pollutants, and is favorable for improving the photocatalytic activity.
FIG. 5 shows a fish scale tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) prepared in example 1 of the present invention2S4/FTCNso) Fish scale tubular carbon nitride (FTCN)so) ZnIn prepared in comparative example 12S4And original nitridingCarbon (g-C)3N4) XPS spectra of (A). In fig. 5, (a) to (G) are diagrams of C1S, N1S, In 3d, Zn 2p, S2 p, XPS valence band and charge differential density In this order. As can be seen from FIG. 5, from the results of the S2 p spectrum (FIG. 5E), it can be confirmed that FTCNsoHas almost no S content and ZnIn2S4This conclusion is further confirmed by the high S2 p content in the 5% composite, thus, the role of trithiocyanuric acid is to build the skeleton, creating pores and defects, rather than introducing S element doping. From another perspective, by comparing monomers and ZnIn2S4/FTCNsoThe XPS element of the composite material can find ZnIn2S4/FTCNsoThe binding energy of the 1n 3d orbitals of the composite has been significantly shifted to that low-field directed motion occurs on the Zn 2p orbitals (the binding energy of the In 3d and Zn 2p orbitals is shifted to the low field). However, FTCNsoAnd ZnIn2S4/FTCNsoThe elemental bonding energies of the composite materials exhibit the opposite trend. ZnIn2S4/FTCNsoThe shift of C1s and N1s in the composite to the high field is small (the binding energy of the C1s and N1s orbitals shift to the high field), which may be due to ZnIn in the composite2S4The content of (A) is low. The binding energy moves due to charge transfer between the two semiconductors. ZnIn2S4/FTCNsoZnIn in (III)2S4Loss of electrons, resulting in transfer of the binding energy of its elements to low fields, and FTCNsoElectrons are acquired, resulting in the transfer of the binding energy of its elements to a high field. To further verify this view, theoretical calculations were used to study the charge differential density of the composite material, and the results are shown in fig. 5G. Near ZnIn2S4FTCNsoThe electron density of the layer is reduced and close to the FTCNsoZnIn of (2)2S4The electron density of the layer increases. In other words, the FTCNsoActing as an electron donor, transferring electrons to an electron acceptor, ZnIn2S4. The theoretical calculation result is consistent with the XPS test conclusion. Thus, g-C3N4In this system electrons are transferred to ZnIn2S4Resulting in a transfer of the binding energy of the composite material. In addition, in order to betterExploring the mechanism of electron transfer, several materials were tested for their valence bands by XPS (fig. 5F). And g-C3N4Comparative, novel FTCNsoThe valence band of the material rises significantly, indicating g-C3N4The band gap structure of the material is changed, which affects the photocatalytic performance of the material.
FIG. 6 shows a fish scale tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) prepared in inventive example 1 and prepared in inventive example 12S4/FTCNso) Fish scale tubular carbon nitride (FTCN)so) ZnIn prepared in comparative example 12S4Tubular Carbon Nitride (TCN) prepared in comparative example 2iso) And raw carbon nitride (g-C)3N4) Ultraviolet-visible diffuse reflectance spectrum of (a). In FIG. 6, (A) - (F) are solid UV-vis DRS spectrogram, light absorption capacity spectrogram of material obtained by theoretical calculation, band gap structure spectrogram of material, FTCNso energy band spectrogram obtained by theoretical calculation, and ZnIn obtained by theoretical calculation in sequence2S4ZnIn obtained by energy band spectrogram and theoretical calculation2S4/FTCNsoBand spectrum. As can be seen from FIG. 6, all samples exhibited strong ultraviolet absorption (. lamda.) (in the above range)<420nm) but clearly different from VSL (λ)>420nm)。FTCNsoThe VSL absorption performance of the material is slightly stronger than that of TCNisoAnd g-C3N4This is due to the special structure (scale porous tubular structure) formed by sufficient self-assembly. As for ZnIn2S4Has strong VSL absorption due to its narrow band gap and thus interacts with FTCNsoCompared with the prior art, the fish scale tubular carbon nitride composite heterojunction photocatalyst (5 percent ZnIn)2S4/FTCNso) Has strong VSL absorption capacity, and the heterojunction material has strong photogenerated carrier capacity easily under VSL irradiation. Meanwhile, the reliability of the optical performance of the prepared material is further verified by the theoretical calculation result. g-C calculated by UV-vis DRS data according to the band gap structure of the material3N4、FTCNso、ZnIn2S4And 5% ZnIn2S4/FTCNsoHave band gaps of 2.72eV and 2eV, respectively64eV, 2.20eV, and 2.50eV (FIG. 6C), consistent with literature reports and theoretical calculations. Similar results can be confirmed from the theoretical calculation results, which also reflects the accuracy of the theoretical calculation model. Thus, FTCNsoAnd ZnIn2S4/FTCNsoAbsorption capacity (. lamda.) of VSL>420nm) is larger than the original g-C3N4And strong, which is beneficial to improving the efficiency of photoproduction electrons and the efficiency of photocatalytic degradation.
FIG. 7 shows a flake tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) prepared in example 1 of the present invention2S4/FTCNso) Fish scale tubular carbon nitride (FTCN)so) ZnIn prepared in comparative example 12S4Tubular Carbon Nitride (TCN) prepared in comparative example 2iso) And raw carbon nitride (g-C)3N4) Electrochemical performance diagram of (1). In FIG. 7, (A) is a photocurrent performance diagram, (B) is a steady-state photoluminescence spectrum, (C) is an impedance diagram, and (D) is a transient photoluminescence spectrum. As can be seen from FIG. 7, 5% ZnIn was irradiated under VSL2S4/FTCNsoHas a transient photocurrent intensity higher than that of FTCNsoAnd g-C3N4Showing the optimum photocurrent intensity (fig. 7A), indicating ZnIn2S4/FTCNsoWith optimum light generation e--h+For separation efficiency, this is probably due to 5% ZnIn2S4/FTCNsoThere are abundant structural defects, ordered tubular structures and wide heterojunction bandgaps. In addition, solid state steady state PL spectroscopy is used to determine the separation efficiency of photogenerated carriers. Based on g-C3N4The photocatalyst of (2) has a distinct absorption peak near 465nm, and at the same time, the PL spectrum of the modified sample has a certain red shift, which further confirms that the band gap has changed. ZnIn2S4Has an absorption peak position of 550 nm. Although ZnIn2S4And 5% ZnIn2S4/FTCNsoHas similar absorption peak intensity, but 5% ZnIn2S4/FTCNsoThe photocurrent response of (fig. 7B) is stronger.
For a good photocatalyst, not only suppression of electrons is requiredAnd holes, and the transfer of electrons and holes must be accelerated. The transfer of electrons is measured by electrochemical impedance EIS (fig. 7C). ZnIn2S4/FTCNsoThe radian of the heterojunction compound is smaller than that of electric arcs of other prepared samples, which shows that the carrier migration resistance of the heterojunction compound is lower, and the photocatalytic activity is favorably improved. Briefly, as a result of photoelectrochemistry, a fish scale tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn)2S4/FTCNso) Has the highest e-h + separation and transfer efficiency, and is beneficial to improving the photocatalytic performance. The electron-hole recombination time was visually observed using transient PL. ZnIn2S4/FTCNsoThe composite material has a longer average decay time than the single semiconductor (fig. 7D), indicating that the presence of the heterojunction interface can effectively accelerate the transfer of photo-generated charge and effectively suppress charge recombination.
It can be seen that the fish scale tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) is compared with other samples2S4/FTCNso) With the highest light generation e--h+This also indicates a fish scale tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) for separation efficiency and excellent photocatalytic performance2S4/FTCNso) The prepared quantum well structure has abundant structural defects, and the synergistic effect of the ordered fish scale tubular structure and the heterojunction interface plays an important role in promoting the separation of photon-generated carriers and prolonging the service life of the carriers.
As shown in FIGS. 1 to 7, in the present invention, ZnIn is surface-modified by using the fish scale tubular carbon nitride as a skeleton2S4The formed fish scale tubular carbon nitride composite heterojunction photocatalyst has the advantages of strong light absorption capacity, low photoproduction electron-hole recombination rate, good photocatalytic performance and the like.
Example 2
The application of the fish scale tubular carbon nitride composite heterojunction photocatalyst in removing organic pollutants in water body specifically is to remove tetracycline hydrochloride in the water body by using the fish scale tubular carbon nitride composite heterojunction photocatalyst, and comprises the following steps:
the fish scale tubular carbon nitride composite heterojunction photocatalyst prepared in example 1 (2% ZnIn)2S4/FTCNso、5％ZnIn2S4/FTCNso、10％ZnIn2S4/FTCNso、50％ZnIn2S4/FTCNso、90％ZnIn2S4/FTCNso、95％ZnIn2S4/FTCNso) Fish scale tubular carbon nitride (FTCN)so) ZnIn prepared in comparative example 12S4Tubular Carbon Nitride (TCN) prepared in comparative example 2iso) And raw carbon nitride (g-C)3N4) Respectively taking 25mg of the tetracycline hydrochloride (TCH) solution, respectively adding the 25mg of the tetracycline hydrochloride (TCH) solution into 50mL of the tetracycline hydrochloride (TCH) solution with the concentration of 10mg/L (the initial pH value of the solution is 6.85), uniformly mixing, adsorbing the tetracycline hydrochloride under the conditions of 30 ℃ and 600rpm, and reaching the adsorption balance after 30 min; placing the mixed solution after reaching the adsorption balance in a xenon lamp (lambda)>420nm), carrying out a photocatalytic reaction for 30min at the temperature of 30 ℃ and the rpm of 600, and finishing the TCH treatment.
FIG. 8 shows a flake tubular carbon nitride composite heterojunction photocatalyst (2% ZnIn) in example 2 of the present invention2S4/FTCNso、5％ZnIn2S4/FTCNso、10％ZnIn2S4/FTCNso、50％ZnIn2S4/FTCNso) Fish scale tubular carbon nitride (FTCN)so)、ZnIn2S4Tubular Carbon Nitride (TCN)iso) And raw carbon nitride (g-C)3N4) The degradation effect of the tetracycline hydrochloride is shown. As can be seen from FIG. 8, in the prepared fish scale tubular carbon nitride composite heterojunction photocatalyst, ZnIn is associated with the prepared fish scale tubular carbon nitride composite heterojunction photocatalyst2S4The increase of the content of the supported metal complex and the adsorption amount of the supported metal complex to tetracycline hydrochloride increase along with the increase of the content of the supported metal complex, which shows that the adsorption capacity of the prepared photocatalyst is along with ZnIn2S4The content is increased because of the benzene ring and ZnIn in tetracycline hydrochloride2S4Zn in (1)2+Have strong metal cation-pi interaction between them, namely ZnIn2S4The tetracycline hydrochloride adsorbent has strong adsorption capacity; however, followZnIn deposition2S4The content is increased, the photocatalytic activity of the fish scale tubular carbon nitride composite heterojunction photocatalyst is firstly increased and reduced, wherein ZnIn2S4When the mass percentage content is less than or equal to 50%, the photocatalytic degradation effect (the data does not include the removal rate of adsorption) of the corresponding fish scale tubular carbon nitride composite heterojunction photocatalyst is obviously higher than that of FTCNsoAnd ZnIn2S4Their arrangement order is 5% ZnIn2S4/FTCNso(74％)>10％ZnIn2S4/FTCNso(72％)>2％ZnIn2S4/FTCNso(71％)>FTCNso(58％)>50％ZnIn2S4/FTCNso(52％)>TCNiso(31％)>ZnIn2S4(17％)>g-C3N4(14%); in addition, ZnIn was tested2S4When the mass percentage content is more than 50%, the photocatalytic degradation effect (the data do not include the removal rate of adsorption) of the corresponding fish scale tubular carbon nitride composite heterojunction photocatalyst is poor, such as 90% ZnIn2S4/FTCNso(33％)、95％ZnIn2S4/FTCNso(21%), which indicates ZnIn2S4The photocatalytic activity of the corresponding fish scale tubular carbon nitride composite heterojunction photocatalyst is obviously higher than that of FTCN when the mass percentage content is less than or equal to 50 percentsoAnd ZnIn2S4In particular, when ZnIn2S4When the mass percentage content is 2-40%, the corresponding fish scale tubular carbon nitride composite heterojunction photocatalyst has better photocatalytic activity, and can degrade and remove organic pollutants in water more quickly and thoroughly. With the original g-C3N4In contrast, FTCN prepared by the novel methodsoThe photocatalytic efficiency of (a) is significantly improved, which may be that the presence of regular structures and rich structural defects improves the bandgap structure, enhances absorption of the VSL and improves the photoelectric properties of the material. It is worth emphasizing that the 5% ZnIn is prepared after two modifications2S4/FTCNsoHas rapid TCH removal efficiency, can remove 85.8 percent (including the removal rate of adsorption, the same below) in 30 minutes, and the ratio of g-C3N4(14.1%) and FTCNso(70.7%) high removal efficiency, probably due to FTCNsoAnd the presence of a heterojunction interface, which facilitates the transport of electrons and e--separation of h +. In short, the synergistic effect between the components improves the absorption of VSL, accelerating e-The separation of-h + and the optimization of the surface and the structure enable the fish scale tubular carbon nitride composite heterojunction photocatalyst to have better photocatalytic performance and can remove antibiotics in water more thoroughly, and other monomer catalysts or tubular carbon nitride photocatalysts cannot achieve the degradation effect.
Meanwhile, in this example, a fish scale tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) was also examined2S4/FTCNso) The degradation effect on tetracycline hydrochloride solutions of different concentrations, different pH values, and different electrolytes (other conditions were the same as in example 2) is shown in FIGS. 9, 10, and 11.
FIG. 9 shows a fish scale tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) in example 2 of the present invention2S4/FTCNso) The degradation effect of the tetracycline hydrochloride solution with different concentrations is shown. As can be seen from FIG. 9, the fish scale tubular carbon nitride composite heterojunction photocatalyst of the invention (5% ZnIn)2S4/FTCNso) After the tetracycline hydrochloride solution with the concentration of 2mg/L, 5mg/L, 10mg/L, 20mg/L and 40mg/L is subjected to photocatalytic reaction for 30min, the degradation efficiency of the tetracycline hydrochloride is 91.43%, 87.82%, 85.80%, 75.63% and 57.65% in sequence, which shows that under high pollutant concentration, the transmission path and light transmittance of a photon-generated carrier are reduced, the migration of the carrier to the active part of a photocatalyst is influenced, and the photocatalytic performance of the carrier is reduced; meanwhile, the intermediate products in the process of the photocatalytic degradation of TCH compete with TCH molecules for limited photocatalytic activity sites, which further results in a decrease in photocatalytic activity. Although high concentrations are detrimental to photocatalytic activity, 5% ZnIn2S4/FTCNsoThe excellent TCH removal photocatalysis performance is still realized under the low pollutant concentration. Considering that the concentration of the contaminants is low in practice, therefore,the invention relates to a fish scale tubular carbon nitride composite heterojunction photocatalyst (5 percent ZnIn)2S4/FTCNso) The tetracycline hydrochloride solution with the concentration less than or equal to 20mg/L has better degradation effect, and can efficiently and thoroughly remove the tetracycline hydrochloride in the water body.
FIG. 10 shows a fish scale tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) in example 2 of the present invention2S4/FTCNso) The degradation effect of the tetracycline hydrochloride solution under different electrolyte conditions is shown. In FIG. 10, the amount of electrolyte added is 1mol per liter of tetracycline hydrochloride solution. As can be seen from FIG. 10, electrolytes (NaCl, Na)2SO4、Na2CO3、Na3PO4) The addition of (A) has an influence on the performance of the catalyst, wherein Cl-and SO-are contained4 2-The addition of (a) has a certain inhibitory effect on photocatalytic degradation, which is probably due to competitive adsorption between the two anions and the TCH; however, addition of CO3 2-And PO3 3-Will strengthen 5% ZnIn2S4/FTCNsoThe adsorption and photocatalytic degradation efficiency of TCH, and the main active substances are changed under the alkaline condition. In summary, the presence of electrolyte is on 5% ZnIn2S4/FTCNsoThe photocatalytic removal of TCH has little effect. Therefore, the fish scale tubular carbon nitride composite heterojunction photocatalyst (5 percent ZnIn) provided by the invention2S4/FTCNso) Can be in NaCl, Na2SO4、Na2CO3、Na3PO4The tetracycline hydrochloride solution with the concentration of 10mg/L is effectively degraded under the interference condition, and the anti-interference capability is better.
FIG. 11 shows a flake tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) in example 2 of the present invention2S4/FTCNso) The degradation effect of the tetracycline hydrochloride solution with different pH values is shown. As can be seen from FIG. 11, the effect on the catalyst performance is different under different pH conditions (initial pH values of 2.28, 4.13, 6.85, 9.18, 11.01), wherein the photocatalytic degradation performance is hardly affected and the photocatalytic degradation performance is not affected under acidic conditionsThere are significant variations. However, it shows a completely different phenomenon in an alkaline environment, and the adsorption property is remarkably improved while the photocatalytic degradation activity is lowered. By combining the photocatalytic Zeta potential and the positively charged characteristic of TCH, we conclude that the electrostatic interaction between the two leads to the improvement of the adsorption performance, which shows that the fish scale tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) of the invention2S4/FTCNso) The method has good adaptability to the pH value of the solution, and particularly has better degradation effect on organic pollutants in the acidic solution.
In order to better analyze the possible mechanism, in this example, the Zeta potential of tetracycline hydrochloride solutions containing different catalysts at different pH values was also measured, and the other conditions were the same as in example 2. The Zeta potential results are shown in FIG. 12.
FIG. 12 shows a tubular carbon nitride composite heterojunction photocatalyst containing fish scales (5% ZnIn) in example 2 of the present invention2S4/FTCNso) Fish scale tubular carbon nitride (FTCN)so)、ZnIn2S4Tubular Carbon Nitride (TCN)iso) And raw carbon nitride (g-C)3N4) Zeta potential maps of tetracycline hydrochloride solutions of different pH values. As can be seen from FIG. 12, the Zeta potential results show that g-C increases with pH3N4、TCNisoAnd FTCNsoMay be due to the TCN of the tubular structureisoAnd FTCNsoHas better electron transmission performance; simultaneously, with FTCNsoAnd Znln2S4Compared with the prior art, the tubular carbon nitride composite heterojunction photocatalyst containing fish scales (5 percent ZnIn)2S4/FTCNso) The Zeta potential of the tetracycline hydrochloride solution also increased, probably due to its availability under acidic conditions.
Further, in this example, a scaly tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) was also examined2S4/FTCNso) The degradation effect of the tetracycline hydrochloride solution with different pH values under different capture agent conditions is also measured, and meanwhile, the fish scale tubular carbon nitride composite heterojunction photocatalysis is also measuredAgent (5% ZnIn)2S4/FTCNso) The conditions for the production of the active ingredient during the treatment of the neutral and basic tetracycline hydrochloride solutions were otherwise the same as in example 2. The results obtained above are shown in fig. 13 and 14.
FIG. 13 shows a fish scale tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) in example 2 of the present invention2S4/FTCNso) The degradation effect of the tetracycline hydrochloride solution with different pH values under different capture agent conditions is shown. In FIG. 13, the capture agent added is disodium ethylenediaminetetraacetate (EDTA-2Na, for capture h)+) Piperidinol oxide (TEMPO, for trapping. O)2 -) Isopropyl alcohol (IPA for trapping. OH), which was used in the reaction system at an initial concentration of 20mM, and pH values of (a), (B), and (C) in fig. 13 were 2.28, 6.85, and 11.01, respectively.
FIG. 14 shows a fish scale tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) in example 2 of the present invention2S4/FTCNso) ESR profile of active ingredient. In FIG. 13, pH values of (A) and (B) are 6.85 and 11.01 in this order.
As can be seen from FIG. 13, h plays the most critical role in the degradation process, O2-is a very important role, and OH has the least effect. Further analysis revealed that, under acidic conditions, the OH content increased due to the presence of a large amount of H +. In alkaline environments, the presence of OH "consumes the major active species h +, thereby reducing its impact on photocatalytic degradation performance. In conclusion, even if the photocatalytic degradation performance under alkaline conditions is reduced, the magnitude of the reduction is small. Therefore, the photocatalyst has good stability in wastewater with different pH values. Meanwhile, as can be seen from FIG. 14, the ESR characterization results also confirmed that. OH and. O2-And the concentration of the active ingredient increases with increasing VSL exposure time.
Example 3
The method for investigating the stability of the fish scale tubular carbon nitride composite heterojunction photocatalyst comprises the following steps:
(1) 50mg of the fish scale tubular carbon nitride photocatalyst (5% ZnIn) obtained in example 1 was taken2S4/FTCNso) Adding into 50mL tetracycline hydrochloride (TCH) solution with concentration of 10mg/L (initial pH of the solution is 6.85), mixing well, adsorbing TCH at 30 deg.C and 600rpm, and reaching adsorption equilibrium after 30 min; placing the mixed solution after reaching the adsorption balance in a xenon lamp (lambda)>420nm and 50W) under the conditions of 30 ℃ and 600rpm for 30min, and finishing the TCH treatment.
(2) And (3) after the treatment in the step (1) is finished, carrying out centrifugal separation on the mixed solution obtained after the degradation is finished at 6000rpm, removing the supernatant obtained by the centrifugal separation, adding 80mL of TCH solution with the concentration of 10mg/L, and repeatedly treating the TCH solution under the same condition as that in the step (1) for 5 times. The tubular carbon nitride photocatalyst (5% ZnIn) of fish scales is measured after each treatment2S4/FTCNso) The results of the degradation efficiency of TCH are shown in FIGS. 15 and 16.
Fig. 15 is a graph showing the mineralization effect of the fish scale tubular carbon nitride composite heterojunction photocatalyst on tetracycline hydrochloride in example 3 of the present invention. As can be seen from fig. 15, after VSL irradiation for 30min, the mineralization efficiency of the fish scale tubular carbon nitride composite heterojunction photocatalyst on TCH reaches 79%, and the fish scale tubular carbon nitride composite heterojunction photocatalyst has good mineralization ability and good application prospect.
Fig. 16 is a graph of the degradation effect of the flake tubular carbon nitride composite heterojunction photocatalyst of the invention in example 3 corresponding to repeated treatment of tetracycline hydrochloride solution. From fig. 16, after the catalyst is repeatedly used for 5 times, the photodegradation efficiency of the fish scale tubular carbon nitride composite heterojunction photocatalyst on the TCH is reduced from 85.8% to 80.3%, which shows that the catalyst has good reusability. From the compositional and structural analysis of the composite, the good reusability was attributed to the FTCNsoTubular skeleton structure and strong Zn2+-pi interaction. The results in fig. 15 and 16 show that the fish scale tubular carbon nitride composite heterojunction photocatalyst has excellent mineralized antibiotic TCH performance and reusability, and has good application potential in practical application.
Example 4
Fish scale tubular carbon nitride composite heterojunction photocatalysisPreparation of the agent in preparation H2O2The application of the method is to prepare H by using the fish scale tubular carbon nitride composite heterojunction photocatalyst to catalyze and oxidize water2O2The method comprises the following steps:
the fish scale tubular carbon nitride composite heterojunction photocatalyst prepared in example 1 (5% ZnIn)2S4/FTCNso) Fish scale tubular carbon nitride (FTCN)so) ZnIn prepared in comparative example 12S4Respectively adding 50mg of the above materials into a mixed solution of 100mL of pure water and 10mL of ethanol, mixing, introducing oxygen at 30 deg.C and 600rpm for 30min, and placing the mixed solution in xenon lamp (lambda)>420nm), carrying out photocatalytic reaction at 30 ℃ and 600rpm for 60min to finish H2O2Is generated.
Control group one: no sacrificial agent is added, and nitrogen is introduced into the reaction system instead of oxygen, and other conditions are the same.
Control group two: without any sacrificial agent, oxygen was introduced under the same conditions.
Control group three: no sacrificial agent is added, oxygen is introduced differently, and other conditions are the same.
FIG. 17 shows a flake tubular carbon nitride composite heterojunction photocatalyst (5% ZnIn) in example 4 of the present invention2S4/FTCNso) Fish scale tubular carbon nitride (FTCN)so)、ZnIn2S4Product of (H)2O2And (5) effect diagrams. In FIG. 17, (A) is the H production of different catalysts2O2Effect diagram, (B) is kinetic spectrogram of different catalysts, (C) is H production under different conditions2O2The effect is compared with the figure.
As can be seen from FIG. 17(A), the photocatalyst prepared produced H2O2The order of the properties is 5% ZnIn2S4/FTCNso>ZnIn2S4>FTCNso. And g-C3N4In contrast, FTCN prepared by the novel methodsoThe photocatalytic efficiency of (A) is significantly improved, which may be the presence of regular structural and abundant structural defects improvesThe band gap structure enhances the absorption of the VSL and improves the photoelectric property of the material. It is worth emphasizing that the photocatalyst prepared after the two-step modification is 5% ZnIn2S4/FTCNsoHas high H yield2O2Performance, H can be within 60 minutes2O2Has a concentration of 135.98. mu. mol L-1Possibly due to the presence of a heterojunction interface, where this facilitates the transport of electrons and e--separation of h +. In short, the synergistic effect between the components improves the absorption of VSL, accelerating e-Separation of h + and optimization of surface and structure. In addition, as shown in FIG. 17(B), H produced by FTCNso2O2Has a Kf significantly lower than that of ZnIn2S4And 5% ZnIn2S4/FTCNsoKf of (1), thus ZnIn2S4The introduction of (b) significantly improves the ZnIn content by 5 percent2S4/FTCNsoH of (A) to (B)2O2Production capacity; meanwhile, 5% ZnIn due to the introduction of FTCNso with small Kd2S4/FTCNsoKd of less than ZnIn2S4Kd of (c), which indicates 5% ZnIn2S4/FTCNsoPromoting ZnIn2S4And decomposition thereof is suppressed. To further understand the photocatalytic production of H2O2Mechanism of (2) to H2O2Was subjected to several comparative experiments (fig. 17C), and the results show that H is found in the decomposition of water without the addition of a sacrificial agent and additional oxygen2O2This shows that a large amount of H can also be generated by photocatalytic degradation without the addition of a sacrificial agent and additional oxygen2O2. Therefore, part of H is generated under VSL irradiation2O2This indicates H2O2Not only by reduction of O by electrons2And also obtained by oxidation, H generated by photogenerated holes2O2. Based on the above conclusions, the production of OH, e-, H + can promote H2O2And further promotes the improvement of photocatalytic degradation performance. Indeed, the presence of hydrogen peroxide generally helps to enhance photocatalyst removalThe nature of the contaminant.
Therefore, the fish scale tubular carbon nitride composite heterojunction photocatalyst (5 percent ZnIn) provided by the invention2S4/FTCNso) Has better photocatalysis performance and can efficiently produce H2O2The photocatalyst has the potential of removing pollutants and sterilizing, and other monomer catalysts or tubular carbon nitride photocatalysts cannot achieve the degradation effect.
Example 5
Investigation of fish scale tubular carbon nitride composite heterojunction photocatalyst decomposition aquatic product H2O2Comprises the following steps:
(1) the fish scale tubular carbon nitride composite heterojunction photocatalyst prepared in example 1 (5% ZnIn)2S4/FTCNso) 50mg, adding into a mixed solution of 100mL of pure water and 10mL of ethanol, mixing uniformly, introducing oxygen for 30min at 30 ℃ and 600rpm, placing the mixed solution after reaching adsorption equilibrium in a xenon lamp (lambda)>420nm), carrying out photocatalytic reaction at 30 ℃ and 600rpm for 60min to finish H2O2Is generated.
(2) After the treatment in step (1) is completed, the mixed solution obtained after the degradation is centrifugally separated at 6000rpm, the supernatant obtained by centrifugation is removed, drying is carried out, and H is repeatedly prepared under the same conditions as in step (1)2O2Repeat for a total of 5 times. Determination of ZnIn after the end of each treatment2S4/FTCNsoProduct of (H)2O2The results are shown in FIG. 18.
FIG. 18 shows the repeated preparation of H by using the flake tubular carbon nitride composite heterojunction photocatalyst in example 5 of the invention2O2The effect diagram of (1). As can be seen from FIG. 18, the hydrogen peroxide productivity after 5 cycles of repeated use was from 135.98. mu. mol L-1The concentration is reduced to 104.92 mu mol L-1Still maintain high photocatalytic H2O2And (4) production performance. In conclusion, the fish scale tubular carbon nitride composite heterojunction photocatalyst has excellent photocatalytic performance of hydrogen peroxide generation and tetracycline degradation, and can be generated in the normal degradation processLarge amount of H2O2And the TCH removal rate is further improved. Therefore, the fish scale tubular carbon nitride composite heterojunction photocatalyst is a promising pollutant degradation and H generation2O2The photocatalyst of (1).
FIG. 19 is a degradation mechanism diagram of the flake tubular carbon nitride composite heterojunction photocatalyst of the present invention. As can be seen from FIG. 19, the mechanism of photocatalytic degradation of antibiotics by the fish scale tubular carbon nitride composite heterojunction photocatalyst is as follows: under the condition of illumination, FTCNsoTransfer of electrons on the conduction band to ZnIn2S4Generating holes, thereby making ZnIn2S4The conduction band of (a) accumulates a large number of electrons. Accumulated in ZnIn2S4The valence band has more and more holes, so the reducibility of the valence band is stronger and the holes are accumulated in ZnIn2S4The conduction band has more and more electrons, so that the oxidation property of the conduction band is stronger and the strong oxidation reduction property can convert oxygen into superoxide radical (O) with strong oxidation property2 -) So that the water is converted into a strongly oxidizing hydroxyl radical (. OH). The final antibiotic is in the form of O with strong oxidizing property2 -And OH, and a reducing cavity is degraded into carbon dioxide and water. As can also be seen from FIG. 19, three radicals (h)+，·O2 -OH) plays an important role in the photodegradation of TCH, where h+Has the greatest effect on TCH degradation, and is secondly O2 -Then OH. And is producing H2O2In the process, O plays the most important role2 -. The reaction equation is as follows:
ZnIn2S4/FTCNso+VSL→ZnIn2S4/FTCNso(e-/h+) (1)
h++OH-→·OH (2)
·OOH+H++e-→H2O2 (5)
H2O2+e-→·OH+OH- (6)
from the above, the fish scale tubular carbon nitride composite heterojunction photocatalyst has the advantages of strong light absorption capacity, low photogenerated electron-hole recombination rate, good photocatalytic performance, good stability and the like, is a novel carbon nitride photocatalytic material, can be widely used for removing organic pollutants (such as antibiotics and dyes) in the environment through photocatalysis, and has good H production2O2Has good performance and application prospect.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (10)
1. The fish scale tubular carbon nitride composite heterojunction photocatalyst is characterized in that the fish scale tubular carbon nitride composite heterojunction photocatalyst takes fish scale tubular carbon nitride as a framework, and the surface of the fish scale tubular carbon nitride is modified with ZnIn2S4(ii) a ZnIn in the fish scale tubular carbon nitride composite heterojunction photocatalyst2S4The mass percentage content of the component (A) is less than or equal to 50 percent.
2. The fish scale tubular carbon nitride composite heterojunction photocatalyst of claim 1The agent is characterized in that ZnIn in the fish scale tubular carbon nitride composite heterojunction photocatalyst2S4The mass percentage of the component (A) is 2-50%.
3. The fish scale tubular carbon nitride composite heterojunction photocatalyst of claim 1 or 2, wherein the fish scale tubular carbon nitride is of a tubular structure, and the surface of the fish scale tubular carbon nitride is composed of fish scales; the ZnIn2S4Is in a flower-shaped spherical structure.
4. A preparation method of the fish scale tubular carbon nitride composite heterojunction photocatalyst as claimed in any one of claims 1 to 3, characterized by comprising the following steps:
(1) sequentially reacting ZnCl2、InCl3Adding thioacetamide into a suspension of fish scale tubular carbon nitride and water, and stirring to obtain a precursor solution;
(2) and (2) carrying out hydrothermal reaction on the precursor solution obtained in the step (1) to obtain the fish scale tubular carbon nitride composite heterojunction photocatalyst.
5. The preparation method of the fish scale tubular carbon nitride composite heterojunction photocatalyst according to claim 4, wherein the preparation method of the fish scale tubular carbon nitride comprises the following steps:
s1, respectively dissolving melamine and trithiocyanuric acid in an organic solvent to obtain a melamine solution and a trithiocyanuric acid solution;
s2, mixing the melamine solution and the trithiocyanuric acid solution obtained in the step S1, and stirring to obtain a mixed solution of melamine and trithiocyanuric acid;
s3, adding water into the mixed solution of melamine and trithiocyanuric acid obtained in the step S2, filtering and drying to obtain a tubular mixture of melamine and trithiocyanuric acid;
s4, calcining the mixture of the tubular melamine and the cyanuric acid obtained in the step S2 to obtain the fish scale tubular carbon nitride.
6. The method for preparing the fish scale tubular carbon nitride composite heterojunction photocatalyst as claimed in claim 5, wherein in step S1, the ratio of the melamine to the organic solvent is 1 g: 30 mL-50 mL; the ratio of the trithiocyanuric acid to the organic solvent is 1 g: 30 mL-50 mL; the organic solvent is at least one of ethanol, N-dimethylformamide and dimethyl sulfoxide;
in the step S2, the molar ratio of melamine to trithiocyanuric acid in the mixed solution of melamine and trithiocyanuric acid is 0.5-1.5: 1; the concentration of melamine in the mixed solution of melamine and trithiocyanuric acid is 0.05-0.15M; the stirring is carried out at the temperature of 20-80 ℃; the rotating speed of the stirring is 600 rpm; the stirring time is 1-4 h;
in the step S3, the volume ratio of the mixed solution of melamine and trithiocyanuric acid to water is 6-10: 5-20; the drying temperature is 70-80 ℃;
in step S4, the calcination is performed in a nitrogen atmosphere or an argon atmosphere; the heating rate in the calcining process is 2.3 ℃/min; the calcining temperature is 450-550 ℃; the calcining time is 2-4 h.
7. The preparation method of the fish scale tubular carbon nitride composite heterojunction photocatalyst as claimed in any one of claims 4 to 6, wherein in the step (1), the precursor solution contains fish scale tubular carbon nitride and ZnCl2、InCl3The mass ratio of the thioacetamide to the thioacetamide is 423: 4.14: 13.12: 6-423: 103.5: 328: 150; the ratio of the fish scale tubular carbon nitride to the water in the suspension of the fish scale tubular carbon nitride and the water is 0.47 g: 80 mL; the stirring time is 2 hours;
in the step (2), the hydrothermal reaction is carried out in a high-pressure reaction kettle; the temperature of the hydrothermal reaction is 180 ℃; the time of the hydrothermal reaction is 12 h.
8. A process as claimed in any one of claims 1 to 3The fish scale tubular carbon nitride composite heterojunction photocatalyst or the fish scale tubular carbon nitride composite heterojunction photocatalyst prepared by the preparation method of any one of claims 4 to 7 is used for removing organic pollutants in water or preparing H2O2The use of (1).
9. The use of claim 8, wherein the scale tubular carbon nitride is used for removing antibiotics in a water body, and comprises the following steps: mixing the fish scale tubular carbon nitride composite heterojunction photocatalyst with water containing organic pollutants, stirring, and carrying out photocatalytic reaction under the condition of illumination to remove the organic pollutants in the water;
the fish scale tubular carbon nitride is used for preparing H2O2The method comprises the following steps: mixing the fish scale tubular carbon nitride composite heterojunction photocatalyst with water, introducing oxygen, and carrying out photocatalytic reaction under the condition of illumination to obtain H2O2。
10. The application of claim 9, wherein when the fish scale tubular carbon nitride is used for removing antibiotics in a water body, the ratio of the fish scale tubular carbon nitride composite heterojunction photocatalyst to the water body containing organic pollutants is 0.5 g-1 g: 1L; the organic pollutants in the water body containing the organic pollutants are antibiotics and/or dyes; the antibiotic is tetracycline hydrochloride; the initial concentration of the organic pollutants in the water body containing the organic pollutants is less than or equal to 20 mg/L; the stirring is carried out under dark conditions; the rotating speed of the stirring is 500-800 rpm; the stirring time is 30 min; the light source adopted in the photocatalytic reaction is a xenon lamp, and the optical power is 45-50W; the photocatalytic reaction is carried out under the stirring condition with the rotating speed of 500 rpm-800 rpm; the temperature of the photocatalytic reaction is 25-35 ℃; the time of the photocatalytic reaction is 30-120 min;
the fish scale tubular carbon nitride is used for preparing H2O2When in use, the ratio of the fish scale tubular carbon nitride composite heterojunction photocatalyst to water is 0.5-1 g: 1L; the oxygen gasIntroducing under dark condition; the introducing time of the oxygen is 30 min; the light source adopted in the photocatalytic reaction is a xenon lamp, and the optical power is 45-50W; the photocatalytic reaction is carried out under the stirring condition with the rotating speed of 500 rpm-800 rpm; the temperature of the photocatalytic reaction is 25-35 ℃; the time of the photocatalytic reaction is 30-120 min; a sacrificial agent is also added into the photocatalytic reaction system; the volume ratio of the sacrificial agent to the water is 1: 10; the sacrificial agent is ethanol and/or isopropanol.
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