CN115193477B - Photocatalyst, and preparation method and application thereof - Google Patents

Photocatalyst, and preparation method and application thereof Download PDF

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CN115193477B
CN115193477B CN202210909697.9A CN202210909697A CN115193477B CN 115193477 B CN115193477 B CN 115193477B CN 202210909697 A CN202210909697 A CN 202210909697A CN 115193477 B CN115193477 B CN 115193477B
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photocatalyst
carbon nitride
attapulgite
atp
pcn
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CN115193477A (en
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张哲�
张楠
聂瑞
方奇绮
葸皎
肖宇轩
师恩槐
周鹏鑫
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Northwest Normal University
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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/063—Polymers comprising a characteristic microstructure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J35/23—
    • B01J35/39—
    • B01J35/51—
    • B01J35/615—
    • B01J35/647—
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/01—Hydrogen peroxide
    • C01B15/027—Preparation from water
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/08—Nanoparticles or nanotubes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention discloses a photocatalyst. The photocatalyst comprises CuInZnS nano particles and an attapulgite/polymer carbon nitride composite material, wherein the content of the CuInZnS nano particles in the photocatalyst is 50-90 wt%, the combination of the CuInZnS nano particles and the attapulgite/polymer carbon nitride composite material is a Z-type heterojunction, and the content of polymer carbon nitride in the attapulgite/polymer carbon nitride composite material is 80-95 wt%. Compared with the existing CuInZnS/g-C3N4 heterojunction, the photocatalyst has better photocatalytic H production 2 O 2 And the ability to photocatalytic reduce Cr (VI).

Description

Photocatalyst, and preparation method and application thereof
Technical Field
The invention belongs toThe field of catalysts, in particular to a Z-type photocatalyst, a preparation method thereof and a method for reducing Cr (VI) and generating H in photocatalysis 2 O 2 Is used in the field of applications.
Background
Hydrogen peroxide (H) 2 O 2 ) As one of ideal resources for solving the energy and environmental pollution, the method is widely applied to the fields of sewage treatment, aquaculture, pulping and papermaking, petrochemical industry and the like. And H is 2 O 2 Can also be used as a clean energy carrier to replace a fuel cell and even replace H in a one-chamber cell 2 Is used for generating electricity. In addition, with clean energy source H 2 In comparison, H 2 O 2 Easier to store and transport and higher in safety, therefore, H 2 O 2 Can be used as a supplementary energy source. However, conventional preparation H 2 O 2 The anthraquinone process has serious environmental problems due to complex production line, high energy input and toxic byproducts. Electrocatalytic preparation of H 2 O 2 Challenges are also presented in terms of serious energy consumption and production safety issues. Thus, how to produce H in green and environment-friendly way 2 O 2 And is also one of the hot spots of research.
Hexavalent chromium compounds belong to a class of carcinogens, have persistent harmfulness to the environment and are easily absorbed by human bodies, and the need for innocent treatment of Cr (VI) containing wastewater, and reduction of Cr (VI) to lower chromium, is one of the modes of innocent treatment.
The Polymer Carbon Nitride (PCN) is used as a carbon-nitrogen material, and has wide application in the aspects of preparing hydrogen, carbon dioxide conversion, photocatalytic degradation of pollutants and the like due to a narrow band gap and a unique structure.
Gan Jianchang in the paper "CuInZnS/g-C 3 N 4 Construction of heterojunction and its photocatalytic Properties (university of Hubei industries, 2021) discloses the selection of CuInZnS and g-C 3 N 4 And compounding, namely, finely adjusting the positions of the energy bands and the forbidden bandwidths of the two semiconductors to obtain the heterojunction with good visible light absorption capacity and energy band matching, so that the visible light catalytic activity is improved. The applicant has to thePhotocatalytic H production of heterojunction 2 O 2 And Cr (VI) reducing performance, and the actual effect is not ideal.
Disclosure of Invention
In view of the above-described deficiencies of the prior art, the present invention provides an improved Z-type photocatalyst for the reduction of Cr (VI) and H production 2 O 2 Exhibits excellent photocatalytic performance.
A photocatalyst comprising CuInZnS nanoparticles and an attapulgite/polymer carbon nitride composite, wherein the content of CuInZnS nanoparticles in the photocatalyst is 50-90 wt%, preferably 65-80 wt%, most preferably 70-75 wt%, the combination of CuInZnS nanoparticles and the attapulgite/polymer carbon nitride composite is a Z-type heterojunction, and the content of polymer carbon nitride in the attapulgite/polymer carbon nitride composite is 80-95 wt%, preferably 90-95 wt%.
Preferably, the molar ratio of Cu, in and Zn In the CuInZnS nano-particles is (0.025-0.1) to 0.2:1.
The preparation method of the photocatalyst comprises the steps of mixing zinc salt, indium salt, cuprous salt, vulcanizing agent and attapulgite/polymer carbon nitride composite material in a water solvent, and then heating in a high-pressure reaction kettle to react to obtain the photocatalyst.
Preferably, the reaction temperature is 150-180 ℃ and the reaction time is 6-8 hours.
Preferably, the zinc salt is zinc acetate, the indium salt is indium acetate, the cuprous salt is cuprous chloride, and the vulcanizing agent is thioacetamide.
Preferably, the attapulgite/polymer carbon nitride composite is obtained by the following method:
and (3) fully mixing the melamine and the attapulgite modified by the silane coupling agent in water, drying, and calcining to obtain the attapulgite/polymer carbon nitride composite material.
Preferably, the calcination temperature is 450-550 ℃ and the time is 4-8 hours.
The photocatalyst can produce H in photocatalysis 2 O 2 Is used in the field of applications.
The application of the photocatalyst in photocatalysis and Cr (VI).
Drawings
Fig. 1 is an electron microscope image and EDS elemental analysis view of a photocatalyst sample.
FIG. 2 is FT-IR and XRD spectra of photocatalyst samples.
Fig. 3 is an XPS spectrum of a photocatalyst sample.
Fig. 4 is an optical performance diagram of the photocatalyst.
FIG. 5 is a BET curve of the photocatalyst.
FIG. 6 is a photocatalytic reduction of Cr (VI) by a photocatalyst and a photocatalytic H production 2 O 2 Is a performance curve of (2).
FIG. 7 is a graph showing the photocatalytic H production by the photocatalyst at various M-ATP/PCN dosages 2 O 2 Is a performance curve of (2).
FIG. 8 is a graph showing the photocatalytic H production of different Cu mole percentages 2 O 2 Is a performance curve of (2).
Detailed Description
The technical scheme of the invention is further described in detail below by combining examples.
Zn(AC) 2 ·2H 2 O zinc acetate dihydrate
In(AC) 3 Indium acetate
TAA thioacetamide
Attapulgite ATP
PCN polymer carbon nitride
M-ATP was prepared as follows: first, ATP was activated using classical methods, 20 g of ATP was added to 200 mL of 1 mol/L HCl, stirred at 80℃for 6h, and then washed with deionized water until no chloride ions were detected. Subsequently, large-particle quartz in ATP was removed with a 800-mesh sieve, and then dried at 105℃to obtain acid-treated ATP (abbreviated as A-ATP). And (3) completely dissolving the 0.4-g 3-aminopropyl triethoxysilane in distilled water, adjusting the pH of the solution to be 3-4 by using 1 mol/L HCl, and performing ultrasonic treatment for 30min to completely hydrolyze the 3-aminopropyl triethoxysilane. Subsequently, 4 g of A-ATP were dispersed in 200 mL absolute ethanol and sonicated for 15 min. Then slowly adding the hydrolyzed 3-aminopropyl triethoxysilane into A-ATP solution, reacting at 80 ℃ for 8 h, then respectively washing with ethanol and deionized water for three times, centrifuging the final sample, and drying at 80 ℃ to obtain the attapulgite (M-ATP for short) modified by the silane coupling agent.
Preparation of M-ATP/PCN composite material: first, M-ATP and melamine were added to 300 mL deionized water at different mass ratios (0.5 g: 5 g,1 g: 5 g), stirred for 30min, and then sonicated for 30min using ultrasound to thoroughly mix them. The mixture was dried at 105 ℃ 12 h and ground to a powder and calcined at 550 ℃ (heating rate 5 ℃/min) 4 h. The products were designated M-ATP/PCN-1 (PCN content: about 90%) and M-ATP/PCN-2 (PCN content: about 83%).
Preparation of PCN: melamine is ground into powder and calcined at 550 ℃ (heating rate 5 ℃/min) for 4 h.
Preparation of ATP/PCN: firstly, ATP and melamine are added into 300 mL deionized water according to the mass ratio (0.5 g:5 g), stirred for 30min, and then treated by ultrasonic waves for 30min so as to be fully mixed. The mixture was dried at 105 ℃ 12 h and ground to a powder and calcined at 550 ℃ (heating rate 5 ℃/min) 4 h.
Preparation of the photocatalyst: 1mmol Zn (AC) was weighed out 2 ·2H 2 O、0.2mmol In(AC) 3 X mmol CuCl (x=0.025, 0.050, 0.075 and 0.100 mmol), adding 20ml deionized water, stirring for half an hour to dissolve, adding 2.5 mmol TAA, stirring for 30min, adding M-ATP/PCN-1 at 20% of total mass fraction of zinc acetate, indium acetate and cuprous chloride, ultrasound for 30min, immediately transferring the mixture to a high-pressure reaction kettle, maintaining at 180deg.C for 6h, cooling to room temperature, collecting the product, washing with absolute ethanol and deionized water three times each, and drying at 60deg.C to obtain photocatalyst (expressed as Cu/In/ZnS-x% @ M-ATP/PCN, wherein x% represents the percentage of the total molar amount of zinc acetate, indium acetate and cuprous chloride) added.
1mmol Zn (AC) was weighed out 2 ·2H 2 O、0.2mmol In(AC) 3 0.025 mmol CuCl, addAdding 20ml of deionized water, stirring for half an hour to dissolve, adding 2.5 mmol of TAA, continuously stirring for 30min, adding M-ATP/PCN-1 according to total mass fractions (10%, 20%, 30% and 40%) of zinc acetate, indium acetate and cuprous chloride respectively, carrying out ultrasonic treatment for 30min, immediately transferring the mixture to a high-pressure reaction kettle, keeping at 180 ℃ for 6h, cooling to room temperature, collecting a product, washing with absolute ethyl alcohol and deionized water three times respectively, and drying at 60 ℃ to obtain the photocatalyst (Cu/In/ZnS@M-ATP/PCN-y%, wherein y% represents the percentage of the mass of M-ATP/PCN to the total mass of zinc acetate, indium acetate and cuprous chloride). The specific examples are shown in Table 2:
TABLE 1 preparation of different photocatalysts
Hereinafter, cuInZnS or CIZS is referred to as Cu/In/ZnS sample
Fig. 1 is an electron microscope image and EDS elemental analysis view of a photocatalyst sample. Fig. 1a is an SEM image of Cu/In/ZnS, the sample consisting of a large number of monodisperse nanospheres with an average size of about 100 nm. As shown In fig. 1b, cu/In/ZnS nanoparticles are tightly embedded In the M-ATP/PCN structure consisting of a large number of pore-like structures, which means that an interface of close contact is formed. FIG. 1c is a low resolution TEM image of Cu/In/ZnS@M-ATP/PCN showing Cu/In/ZnS nanoparticles distributed on the support M-ATP/PCN, which is consistent with the image of SEM. Lattice fringes were seen In the high resolution TEM image of FIG. 1d, with a lattice constant of 0.31nm, indicating Cu/In/ZnS growth on the M-ATP/PCN surface. As shown in fig. 1e, energy Dispersive Spectroscopy (EDS) further confirmed that the components of the synthetic samples were carbon, nitrogen, copper, indium, zinc and sulfur.
FIG. 2 is FT-IR and XRD spectra of photocatalyst samples. FIGS. 2a-b show that the infrared characteristic peaks of the Cu/In/ZnS@M-ATP/PCN composite material are similar to those of the M-ATP/PCN, which shows that the chemical structure of the M-ATP/PCN is not destroyed In the sample preparation process, and the characteristic peaks of the M-ATP/PCN are gradually enhanced with the increase of the doping amount of the M-ATP/PCN, and the characteristic peaks are slightly offset, which shows that the M-ATP/PCN and the Cu/In/ZnS are not simply physically doped, but form chemical bonds. FIGS. 2c-d show that as the M-ATP/PCN incorporation increases, the diffraction peaks do not shift, indicating that the M-ATP/PCN doping does not affect the crystallinity of Cu/In/ZnS, three major diffraction peaks at 28.6 °, 47.6℃and 56.5℃correspond to (111), (220) and (311) crystal planes, respectively, and a characteristic peak at 8.52℃corresponds to attapulgite. The two characteristic peaks at 13.7 ° and 27.4 ° correspond to the (100) and (002) crystal planes of PCN.
FIG. 3 shows XPS spectra of photocatalyst samples, (a) C1S, (b) N1S, (C) S2 p, (d) Zn 2p, (e) In 3d, and (f) Cu 2p. The C1s spectrum of FIG. 3a shows that the Cu/In/ZnS@M-ATP/PCN-20% peak areas of 288.18 eV and 286.78 eV are significantly reduced, while the peak area of 284.78 eV is significantly increased, probably due to the formation of chemical bonds between M-ATP/PCN and Cu/In/ZnS. In the N1s spectrum of FIG. 3b, the characteristic peak of Cu/In/ZnS@M-ATP/PCN-20% shifted forward compared to that of M-ATP/PCN and was accompanied by a change In peak area due to the influence of Cu/In/ZnS. These results clearly demonstrate that the heterojunction structure formed between Cu/In/ZnS and M-ATP/PCN is not a simple physical mix.
FIG. 4 is a graph of optical performance of a photocatalyst, (a) ultraviolet visible spectrum, (b) PL spectrum, (c) Tauc graph, (d) time resolved fluorescence decay spectrum, (e) transient photocurrent response, and (f) EIS impedance spectrum. FIG. 4a shows that the absorption edge of the M-ATP/PCN sample shows a red shift compared to PCN, due to the successful doping of M-ATP. The absorption strength of the Cu/In/ZnS@M-ATP/PCN-20% sample is obviously enhanced (lambda)>420 nm), which indicates that the photocatalyst has better absorption to visible light, and is favorable for generating more photo-generated electrons and holes. In fig. 4b, the PCN sample shows a strong fluorescence signal, whereas the fluorescence intensity of the Cu/In/zns@m-ATP/PCN-20% sample is much weaker, indicating that the recombination process effectively suppresses the recombination of photogenerated carriers. FIG. 4c is according to (ah v) 2 The relation between (hν) and (h v) calculated the optical bandgaps, the bandgaps of the PCN, M-ATP/PCN, cu/In/ZnS and Cu/In/ZnS@M-ATP/PCN-20% composites were 3.02 eV, 2.78 eV, 3.18 eV and 2.42 eV, respectively. FIG. 4d shows that the transient fluorescence lifetimes of Cu/In/ZnS and Cu/In/ZnS@M-ATP/PCN-20% are 2.18 and 1.87. 1.87 ns, respectively.
FIG. 5Is the BET curve of the photocatalyst. PCN, M-ATP/PCN and Cu/In/ZnS samples were identified as type iv isotherms of the H3 hysteresis loop, indicating the presence of mesopores. The Cu/In/ZnS@M-ATP/PCN sample is an I type isotherm, and the average pore size is about 3.204 nm and is far smaller than that of other samples. The specific surface areas of the PCN, M-ATP/PCN, cu/In/ZnS and Cu/In/ZnS@M-ATP/PCN samples were 10.28, 30.24, 95.38, 199.9M, respectively 2 /g。
Photocatalytic Performance test
(1) Photocatalytic reduction of Cr (vi) in air atmosphere: 10 mg photocatalyst is weighed, 50 mL of Cr (VI) solution (20 mg/L) is added, the mixture is stirred for 30 minutes under dark condition to reach adsorption-desorption equilibrium, light irradiation is started, suspension is collected every 10 minutes, and the concentration of Cr (VI) is measured by adopting a dibenzoyl dihydrazide spectrophotometry. 1mL of the supernatant was taken and added with 9mL of deionized water, 0.1mL of 9.2M H 2 SO 4 Solution, 0.1mL of 7.3M H 3 PO 4 The solution was injected into a glass bottle. Then, the dibenzoyl dihydrazide solution 0.4. 0.4 mL was mixed with the above mixed solution, and after several minutes, a purple solution was formed, and the absorbance thereof was measured at 540. 540 nm.
(2) Photocatalytic production of H in air atmosphere 2 O 2 : 20mg of the photocatalyst was weighed and dispersed in 40mL of the mixed solution (36 mL of ultrapure water and 4mL of isopropyl alcohol as a sacrificial agent). Stir under dark conditions for 30 minutes. The visible light source is provided by a 300W Xe lamp with a 420 nm cutoff filter. During the light irradiation, the sample was collected every 5 min and filtered through a 0.45 μm microporous filter. Determination of H by iodometry 2 O 2 Is contained in the composition. To the collected 2 mL solution was added 1mL of 0.1 mol L -1 C 8 H 5 KO 4 And 0.4 mol L -1 KI aqueous solution was adequately colored for 30min, and H was measured at 350 nm 2 O 2 Is contained in the composition.
As shown In FIG. 6a, after the adsorption equilibrium is reached under dark conditions, the adsorption capacity of the Cu/In/ZnS and Cu/In/ZnS@M-ATP/PCN-20% samples for Cr (VI) is large, while the M-ATP/PCN adsorption capacity is very low. After irradiation with visible light for 40 min, the reduction rate of Cr (VI) In M-ATP/PCN is only 1.6%, while the reduction rate of Cu/In/ZnS@M-ATP/PCN-20% on Cr (VI) is more than 99.3%, which is far higher than that of M-ATP/PCN and is 1.11 times that of Cu/In/ZnS. FIG. 6b shows the determination of the removal of the active species during photocatalytic reduction of Cr (VI). FIG. 6c is a cycling experiment of the photocatalyst for photocatalytic reduction of Cr (VI).
As shown in FIG. 6d, after 30min of photocatalysis, the M-ATP/PCN sample produced H 2 O 2 The amount of (2) is very small and can be ignored. However, cu/In/ZnS@M-ATP/PCN-20% catalyst-produced H 2 O 2 The amount of (C) is 372.63 mu mol.L -1 Is a Cu/In/ZnS sample (139.83. Mu. Mol.L) -1 ) Is 56.03 times that of the M-ATP/PCN sample. As shown in FIG. 6e, when O is introduced into the reaction solution 2 At the time of Cu/In/ZnS@M-ATP/PCN-20% of catalyst H 2 O 2 The yield is increased, and the result shows that the oxygen plays an important role in the photocatalysis process. In addition, the Cu/In/ZnS@M-ATP/PCN-20% sample has higher specific surface area, which is beneficial to capturing O 2 So that H 2 O 2 The yield of (2) is significantly improved. FIG. 6f shows photocatalytic H production by a photocatalyst 2 O 2 Is a cyclic experiment of (a).
The invention simultaneously tests Cu/In/ZnS@PCN-20%, cu/In/ZnS@ATP/PCN-20%, and CIZS (1-3)/CCN In the above document for photocatalytic reduction of Cr (VI) and photocatalytic production of H under the same conditions 2 O 2 The specific results are shown in the following table.
Note that: 47% CIZS (1-3)/CCN reference "CuInZnS/g-C 3 N 4 Construction of heterojunction and its photocatalytic properties "(Gan Jianchang, university of Hubei industries, 2021). Other samples were prepared as described in Table 2 above.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. Photocatalyst for producing H in photocatalysis 2 O 2 Or in the photocatalytic reduction of Cr (VI), wherein the photocatalyst comprises CuInZnS nano particles and an attapulgite/polymer carbon nitride composite material, the content of the CuInZnS nano particles in the photocatalyst is 50-90 wt%, the combination of the CuInZnS nano particles and the attapulgite/polymer carbon nitride composite material is a Z-type heterojunction, the content of polymer carbon nitride in the attapulgite/polymer carbon nitride composite material is 80-95 wt%,
the photocatalyst is prepared by a method comprising the following steps:
mixing zinc salt, indium salt, cuprous salt, vulcanizing agent and attapulgite/polymer carbon nitride composite material in a water solvent, and then heating in a high-pressure reaction kettle to react to obtain the photocatalyst;
the attapulgite/polymer carbon nitride composite material is prepared by the following steps:
and (3) fully mixing the melamine and the attapulgite modified by the silane coupling agent in water, drying, and calcining to obtain the attapulgite/polymer carbon nitride composite material.
2. The use according to claim 1, characterized in that: the content of the CuInZnS nano particles in the photocatalyst is 65-80 wt%;
the content of the polymer carbon nitride in the attapulgite/polymer carbon nitride composite material is 90-95 wt%.
3. The use according to claim 2, characterized in that: the content of the CuInZnS nano particles in the photocatalyst is 70-75wt%.
4. The use according to claim 1, characterized in that: the molar ratio of Cu, in and Zn In the CuInZnS nano particles is (0.025-0.1): 0.2:1.
5. The use according to claim 1, characterized in that: the reaction temperature is 150-180 ℃ and the reaction time is 6-8 hours.
6. The use according to claim 1, characterized in that: the zinc salt is zinc acetate, the indium salt is indium acetate, the cuprous salt is cuprous chloride, and the vulcanizing agent is thioacetamide.
7. The use according to claim 1, characterized in that: the calcination temperature is 450-550 ℃ and the calcination time is 4-8 hours.
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