CN111330602A - Carbon cloth loaded BiOCl/BiVO4Recyclable flexible composite photocatalytic material, preparation method and application - Google Patents
Carbon cloth loaded BiOCl/BiVO4Recyclable flexible composite photocatalytic material, preparation method and application Download PDFInfo
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- CN111330602A CN111330602A CN202010215888.6A CN202010215888A CN111330602A CN 111330602 A CN111330602 A CN 111330602A CN 202010215888 A CN202010215888 A CN 202010215888A CN 111330602 A CN111330602 A CN 111330602A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 97
- 239000004744 fabric Substances 0.000 title claims abstract description 95
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 66
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 54
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000001035 drying Methods 0.000 claims abstract description 40
- 238000005406 washing Methods 0.000 claims abstract description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 34
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000000151 deposition Methods 0.000 claims abstract description 18
- 238000002791 soaking Methods 0.000 claims abstract description 16
- 229910019501 NaVO3 Inorganic materials 0.000 claims abstract description 15
- 238000004140 cleaning Methods 0.000 claims abstract description 14
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- 239000008367 deionised water Substances 0.000 claims description 37
- 229910021641 deionized water Inorganic materials 0.000 claims description 37
- 239000003344 environmental pollutant Substances 0.000 claims description 25
- 231100000719 pollutant Toxicity 0.000 claims description 25
- 239000002243 precursor Substances 0.000 claims description 24
- 230000008021 deposition Effects 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 13
- 238000010306 acid treatment Methods 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000007598 dipping method Methods 0.000 claims description 12
- 239000004519 grease Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000004729 solvothermal method Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 238000007654 immersion Methods 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 230000020477 pH reduction Effects 0.000 claims 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims 1
- 239000011941 photocatalyst Substances 0.000 abstract description 8
- 230000031700 light absorption Effects 0.000 abstract description 6
- 239000000843 powder Substances 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 33
- 238000002835 absorbance Methods 0.000 description 22
- 230000015556 catabolic process Effects 0.000 description 15
- 238000006731 degradation reaction Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000005286 illumination Methods 0.000 description 11
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 11
- 229940043267 rhodamine b Drugs 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 11
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 11
- 238000000926 separation method Methods 0.000 description 10
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- 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
- B01J27/06—Halogens; Compounds thereof
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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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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- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2305/10—Photocatalysts
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Abstract
Preparation of carbon cloth loaded BiOCl/BiVO4The method for recycling the flexible composite photocatalytic material comprises the following steps: and (3) cleaning the carbon cloth in an acetone solution, soaking the carbon cloth in a concentrated hydrochloric acid solution for 8 hours, washing the carbon cloth with water, and drying the carbon cloth. Adding Bi (NO)3)3·5 H2O and NaVO3·2 H2Dissolving O in glycerol and water respectively; after mixing, transferring the mixture into a high-pressure kettle and keeping the temperature at 180 ℃ for 8 h; drying to obtain BiVO4And (3) powder. Placing carbon cloth in BiVO4In the solution, depositing to obtain the carbon cloth loaded BiOCl/BiVO4The flexible composite photocatalytic material can be recycled. The invention takes the carbon cloth as the substrate and shows excellent conductivity, flexibility and bendabilityThe method has the advantages of high carrier diffusion rate, wide photoresponse range, recyclability and low cost, overcomes the defects of low BiOCl light absorption and large energy loss, can effectively solve the problem that the existing powder photocatalyst is difficult to separate and recycle, and realizes sustainable development of resources.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a method for preparing carbon cloth loaded BiOCl/BiVO4A method for recovering a flexible composite photocatalytic material and application thereof.
Background
The semiconductor material is an effective energy production technology for photocatalytic decomposition of water and degradation of organic pollutants, can replace fossil fuels and carry out environmental remediation, and is expected to solve the problems of world energy shortage and environmental pollution. Because of the abundant bismuth output in China, the bismuth group photocatalyst has higher photocatalytic efficiency, thereby causing extensive attention of researchers.
In recent years, BiOCl has attracted much attention in the fields of photocatalytic organic pollutant degradation and water oxidation due to its suitable valence band position and specific layered structure (Cl-O-Bi-O-Cl). However, the low charge separation rate and poor stability still limit the wide application of BiOCl in photolysis of water and degradation of pollutants. Therefore, how to enhance the photogenerated charge separation and photochemical stability of BiOCl to perform effective photocatalytic reactions becomes a major problem in current research. In order to improve the charge separation efficiency, researchers combine BiOCl with Ag, Au, carbon quantum dots and the like to construct a heterojunction; due to the unique two-dimensional planar structure and abundant surface groups of the RGO and the electron accepting and transferring capability of the RGO, the BiOCl/RGO heterojunction further improves the photocatalytic performance of the BiOCl under ultraviolet irradiation.
Bismuth vanadate (BiVO)4) The forbidden band width of the material is 2.3-2.4eV, the material can decompose water and degrade pollutants under visible light, and the material has the characteristics of wide photoresponse range, low carbon, environmental protection and no toxicity. However, the photodegradation efficiency is limited because the photo-generated electrons and holes are easily recombined and the quantum efficiency is low. Accordingly, BiVO with high photogenerated carrier separation efficiency, wide range of visible light response and low cost is developed4Matrix composites remain of great interest and challenge.
The performance and application of a single semiconductor material generally have great limitations and cannot meet various requirements of actual production. By loading metals or metal oxides, e.g. V, on their surfaces2O5/BiVO4、Cu/BiVO4、CeO2/BiVO4And the like, a built-in electric field is formed in the material to promote the separation of photon-generated carriers, thereby improving the photocatalytic activity.
Although these measures are effective in improving photocatalytic activity, the nanocomposite powder is difficult to recover during the application of photocatalytic water treatment, which causes secondary pollution and limits its practical application. Therefore, how to ensure the stability of the photocatalyst and reduce the difficulty of recovery is a problem to be solved at present.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing carbon cloth loaded BiOCl/BiVO4Method for recycling flexible composite photocatalytic material, application of method and carbonCloth-loaded BiOCl/BiVO4The recyclable flexible composite photocatalytic material takes simple and easily-obtained carbon cloth as a substrate, shows excellent conductivity, flexibility and bendability, does not need to worry about material damage even if being folded for a long time or repeatedly bent, can be cut according to different use environments, has the advantages of high carrier diffusion rate, wide photoresponse range, recyclability, good cycle performance and low cost, overcomes the defects of low BiOCl light absorption and large energy loss, solves the problem of difficult separation and recovery of a powder photocatalyst, and realizes sustainable development and cyclic utilization of resources.
In order to achieve the purpose, the invention adopts the technical scheme that:
preparation of carbon cloth loaded BiOCl/BiVO4The method for recycling the flexible composite photocatalytic material comprises the following steps: cleaning carbon cloth in acetone solution for 30 min to remove impurities such as oil and wax on the surface, soaking in concentrated hydrochloric acid solution at room temperature for 8 h, washing with water, and drying for 6 h. A certain molar amount of Bi (NO)3)3·5 H2Dissolving O in glycerol; a certain molar weight of NaVO3·2 H2Dissolving O in deionized water; mixing the above solutions and transferring into an autoclave with a polytetrafluoroethylene lining, and keeping at 180 ℃ for 8 h; centrifuging, washing with water, washing with alcohol, and drying at 60 deg.C for 4 h to obtain BiVO4And (3) powder. Placing carbon cloth in the BiVO4In the solution, the carbon cloth loaded BiOCl/BiVO is obtained after a certain time of deposition4The flexible composite photocatalytic material can be recycled.
The method comprises the following steps:
cleaning 5 x 5 cm carbon cloth in acetone solution for 30 min to remove impurities such as grease and wax on the surface;
step two:
soaking the carbon cloth in concentrated hydrochloric acid solution at room temperature for 8 h;
step three:
washing the carbon cloth subjected to acid treatment with water, and drying at 60 ℃ for 6 h to obtain a sample A;
step four:
0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution B;
adding 0.4 mmol of NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution C;
step five:
adding the solution C into the solution B and stirring vigorously to obtain a solution D; transferring the solution D into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 180 ℃ for 8 hours to obtain a synthetic product E;
step six:
centrifuging and separating the solvent thermal synthesis product E at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product F;
step seven:
1G of product F is dissolved in 100 ml of water to give a solution G;
step eight:
dipping the sample A in the solution G, carrying out ultrasonic deposition for 12 h, washing with deionized water and ethanol, and drying at 60 ℃ for 3h to obtain the carbon cloth loaded BiOCl/BiVO4The flexible composite photocatalytic material can be recycled.
And in the second step, the soaking time is 1-12 hours.
And in the fifth step, the temperature range of the solvent is 120-200 ℃.
And in the fifth step, the solvent heating time is 6-12 h.
And the mass range of the product F in the seventh step is 0.1-1.5 g.
The deposition time in the step eight is 3-15 h.
Carbon cloth loaded BiOCl/BiVO4The recyclable flexible composite photocatalytic material is applied to photocatalytic technologies, such as pollutant degradation, photolysis water and the like. A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B (Rh B) solution is measured and added with the catalyst. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, taking 4 mL samples from the reaction vessel every 20 min, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging catalysis according to the absorbanceThe efficiency of the agent in degrading the contaminant solution.
The invention has the beneficial effects that:
the invention adopts carbon cloth as a flexible substrate to prepare the carbon cloth loaded BiOCl/BiVO4The recyclable flexible composite photocatalytic material has high conductivity, flexibility and bendability, does not need to worry about material damage even if being folded for a long time or repeatedly bent, and has the advantages of high charge separation rate, wide light absorption range, high photocatalytic activity, high degradation rate and strong hydrolysis capacity.
For BiVO4The invention utilizes the excellent conductivity of the carbon cloth and the BiVO4And the synergistic effect of the BiOCl can accelerate the transmission speed of current carriers, reduce the recombination rate of photo-generated electron holes, improve the defects of low light absorption, low charge separation rate, poor stability and large energy loss of the BiOCl, and ensure that the preparation process is simple and convenient to operate, energy-saving and environment-friendly.
In addition, the problem of recovery and reuse of the photocatalyst must be solved in practical use, and thus the photocatalyst should be fixed on some substrate. The carbon cloth used in the invention is convenient and easy to obtain, has excellent conductivity and physical and mechanical properties, facilitates the recycling of the photocatalyst, and solves the current situations that the powdery catalyst is difficult to recycle and reuse.
Drawings
FIG. 1 shows that BiOCl/BiVO is loaded on carbon cloth4A preparation flow chart and a sample schematic diagram of the recyclable flexible composite photocatalytic material.
FIG. 2 shows BiVO obtained4And carbon cloth loaded BiOCl/BiVO4The XRD image of the flexible composite photocatalytic material can be recovered.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1
(1) Cleaning 5 x 5 cm carbon cloth in acetone solution for 30 min to remove impurities such as grease and wax on the surface;
(2) soaking the carbon cloth in concentrated hydrochloric acid solution at room temperature for 8 h;
(3) washing the carbon cloth subjected to acid treatment with water, and drying at 60 ℃ for 6 h to obtain a sample A;
(4) 0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution B; adding 0.4 mmol NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution C;
(5) adding the solution C into the solution B, violently stirring to obtain a solution D, transferring the solution D into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 180 ℃ for 8 hours to obtain a synthetic product E;
(6) centrifuging and separating the solvent thermal synthesis product E at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product F;
(7) 1G of product F is dissolved in 100 ml of water to give a solution G;
(8) dipping the sample A in the solution G, carrying out ultrasonic deposition for 12 h, washing with deionized water and ethanol, and drying at 60 ℃ for 3h to obtain the carbon cloth loaded BiOCl/BiVO4The flexible composite photocatalytic material can be recycled.
The obtained carbon cloth loaded BiOCl/BiVO4The method for testing the photocatalytic performance of the recyclable flexible composite photocatalytic material comprises the following steps:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B (Rh B) solution is measured and added with the catalyst. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, taking 4 mL samples from the reaction vessel every 20 min, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst on the pollutant solution according to the absorbance.
Example 2
(1) Cleaning 5 x 5 cm carbon cloth in acetone solution for 30 min to remove impurities such as grease and wax on the surface;
(2) soaking the carbon cloth in concentrated hydrochloric acid solution at room temperature for 10 h;
(3) washing the carbon cloth subjected to acid treatment with water, and drying at 60 ℃ for 6 h to obtain a sample A;
(4) 0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution B; adding 0.4 mmol NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution C;
(5) adding the solution C into the solution B, violently stirring to obtain a solution D, transferring the solution D into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 200 ℃ for 12 hours to obtain a synthetic product E;
(6) centrifuging and separating the solvent thermal synthesis product E at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product F;
(7) 1.5G of product F was dissolved in 100 ml of water to give solution G;
(8) dipping the sample A in the solution G, carrying out ultrasonic deposition for 15 h, washing with deionized water and ethanol, and drying at 60 ℃ for 3h to obtain the carbon cloth loaded BiOCl/BiVO4The flexible composite photocatalytic material can be recycled.
The obtained carbon cloth loaded BiOCl/BiVO4The method for testing the photocatalytic performance of the recyclable flexible composite photocatalytic material comprises the following steps:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B (Rh B) solution is measured and added with the catalyst. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, taking 4 mL samples from the reaction vessel every 20 min, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst on the pollutant solution according to the absorbance.
Example 3
(1) Cleaning 5 x 5 cm carbon cloth in acetone solution for 30 min to remove impurities such as grease and wax on the surface;
(2) soaking the carbon cloth in concentrated hydrochloric acid solution at room temperature for 6 h;
(3) washing the carbon cloth subjected to acid treatment with water, and drying at 60 ℃ for 6 h to obtain a sample A;
(4) adding 0.4 mmol of Bi(NO3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution B; adding 0.4 mmol NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution C;
(5) adding the solution C into the solution B, violently stirring to obtain a solution D, transferring the solution D into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 160 ℃ for 8 hours to obtain a synthetic product E;
(6) centrifuging and separating the solvent thermal synthesis product E at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product F;
(7) 0.5G of product F was dissolved in 100 ml of water to give solution G;
(8) dipping the sample A in the solution G, carrying out ultrasonic deposition for 9 h, washing with deionized water and ethanol, and drying at 60 ℃ for 3h to obtain the carbon cloth loaded BiOCl/BiVO4The flexible composite photocatalytic material can be recycled.
The obtained carbon cloth loaded BiOCl/BiVO4The method for testing the photocatalytic performance of the recyclable flexible composite photocatalytic material comprises the following steps:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B (Rh B) solution is measured and added with the catalyst. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, taking 4 mL samples from the reaction vessel every 20 min, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst on the pollutant solution according to the absorbance.
Example 4
(1) Cleaning 5 x 5 cm carbon cloth in acetone solution for 30 min to remove impurities such as grease and wax on the surface;
(2) soaking the carbon cloth in concentrated hydrochloric acid solution at room temperature for 4 h;
(3) washing the carbon cloth subjected to acid treatment with water, and drying at 60 ℃ for 6 h to obtain a sample A;
(4) 0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution B; adding 0.4 mmol NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution C;
(5) adding the solution C into the solution B, violently stirring to obtain a solution D, transferring the solution D into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 120 ℃ for 8 hours to obtain a synthetic product E;
(6) centrifuging and separating the solvent thermal synthesis product E at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product F;
(7) 0.1G of product F was dissolved in 100 ml of water to give solution G;
(8) dipping the sample A in the solution G, carrying out ultrasonic deposition for 3h, washing with deionized water and ethanol, and drying at 60 ℃ for 3h to obtain the carbon cloth loaded BiOCl/BiVO4The flexible composite photocatalytic material can be recycled.
The obtained carbon cloth loaded BiOCl/BiVO4The method for testing the photocatalytic performance of the recyclable flexible composite photocatalytic material comprises the following steps:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B (Rh B) solution is measured and added with the catalyst. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, taking 4 mL samples from the reaction vessel every 20 min, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst on the pollutant solution according to the absorbance.
Example 5
(1) Cleaning 5 x 5 cm carbon cloth in acetone solution for 30 min to remove impurities such as grease and wax on the surface;
(2) soaking the carbon cloth in concentrated hydrochloric acid solution at room temperature for 1 h;
(3) washing the carbon cloth subjected to acid treatment with water, and drying at 60 ℃ for 6 h to obtain a sample A;
(4) 0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution B; adding 0.4 mmol NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution C;
(5) adding the solution C into the solution B, violently stirring to obtain a solution D, transferring the solution D into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 180 ℃ for 8 hours to obtain a synthetic product E;
(6) centrifuging and separating the solvent thermal synthesis product E at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product F;
(7) dissolving 0.3G of product F in 100 ml of water to obtain solution G;
(8) dipping the sample A in the solution G, carrying out ultrasonic deposition for 6 h, washing with deionized water and ethanol, and drying at 60 ℃ for 3h to obtain the carbon cloth loaded BiOCl/BiVO4The flexible composite photocatalytic material can be recycled.
The obtained carbon cloth loaded BiOCl/BiVO4The method for testing the photocatalytic performance of the recyclable flexible composite photocatalytic material comprises the following steps:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B (Rh B) solution is measured and added with the catalyst. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, taking 4 mL samples from the reaction vessel every 20 min, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst on the pollutant solution according to the absorbance.
Example 6
(1) Cleaning 5 x 5 cm carbon cloth in acetone solution for 30 min to remove impurities such as grease and wax on the surface;
(2) soaking the carbon cloth in concentrated hydrochloric acid solution at room temperature for 2 h;
(3) washing the carbon cloth subjected to acid treatment with water, and drying at 60 ℃ for 6 h to obtain a sample A;
(4) 0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution B; adding 0.4 mmol NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution C;
(5) adding the solution C into the solution B, violently stirring to obtain a solution D, transferring the solution D into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 180 ℃ for 6 hours to obtain a synthetic product E;
(6) centrifuging and separating the solvent thermal synthesis product E at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product F;
(7) 1G of product F is dissolved in 100 ml of water to give a solution G;
(8) dipping the sample A in the solution G, carrying out ultrasonic deposition for 9 h, washing with deionized water and ethanol, and drying at 60 ℃ for 3h to obtain the carbon cloth loaded BiOCl/BiVO4The flexible composite photocatalytic material can be recycled.
The obtained carbon cloth loaded BiOCl/BiVO4The method for testing the photocatalytic performance of the recyclable flexible composite photocatalytic material comprises the following steps:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B (Rh B) solution is measured and added with the catalyst. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, taking 4 mL samples from the reaction vessel every 20 min, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst on the pollutant solution according to the absorbance.
Example 7
(1) Cleaning 5 x 5 cm carbon cloth in acetone solution for 30 min to remove impurities such as grease and wax on the surface;
(2) soaking the carbon cloth in concentrated hydrochloric acid solution at room temperature for 6 h;
(3) washing the carbon cloth subjected to acid treatment with water, and drying at 60 ℃ for 6 h to obtain a sample A;
(4) 0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution B; adding 0.4 mmol NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution C;
(5) adding the solution C into the solution B, violently stirring to obtain a solution D, transferring the solution D into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 160 ℃ for 8 hours to obtain a synthetic product E;
(6) centrifuging and separating the solvent thermal synthesis product E at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product F;
(7) 0.5G of product F was dissolved in 100 ml of water to give solution G;
(8) dipping the sample A in the solution G, carrying out ultrasonic deposition for 3h, washing with deionized water and ethanol, and drying at 60 ℃ for 3h to obtain the carbon cloth loaded BiOCl/BiVO4The flexible composite photocatalytic material can be recycled.
The obtained carbon cloth loaded BiOCl/BiVO4The method for testing the photocatalytic performance of the recyclable flexible composite photocatalytic material comprises the following steps:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B (Rh B) solution is measured and added with the catalyst. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, taking 4 mL samples from the reaction vessel every 20 min, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst on the pollutant solution according to the absorbance.
Example 8
(1) Cleaning 5 x 5 cm carbon cloth in acetone solution for 30 min to remove impurities such as grease and wax on the surface;
(2) soaking the carbon cloth in concentrated hydrochloric acid solution at room temperature for 1 h;
(3) washing the carbon cloth subjected to acid treatment with water, and drying at 60 ℃ for 6 h to obtain a sample A;
(4) 0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution B; adding 0.4 mmol NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution C;
(5) adding the solution C into the solution B, violently stirring to obtain a solution D, transferring the solution D into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 180 ℃ for 10 hours to obtain a synthetic product E;
(6) centrifuging and separating the solvent thermal synthesis product E at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product F;
(7) 1G of product F is dissolved in 100 ml of water to give a solution G;
(8) dipping the sample A in the solution G, carrying out ultrasonic deposition for 12 h, washing with deionized water and ethanol, and drying at 60 ℃ for 3h to obtain the carbon cloth loaded BiOCl/BiVO4The flexible composite photocatalytic material can be recycled.
The obtained carbon cloth loaded BiOCl/BiVO4The method for testing the photocatalytic performance of the recyclable flexible composite photocatalytic material comprises the following steps:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B (Rh B) solution is measured and added with the catalyst. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, taking 4 mL samples from the reaction vessel every 20 min, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst on the pollutant solution according to the absorbance.
Example 9
(1) Cleaning 5 x 5 cm carbon cloth in acetone solution for 30 min to remove impurities such as grease and wax on the surface;
(2) soaking the carbon cloth in concentrated hydrochloric acid solution at room temperature for 4 h;
(3) washing the carbon cloth subjected to acid treatment with water, and drying at 60 ℃ for 6 h to obtain a sample A;
(4) 0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution B; adding 0.4 mmol NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution C;
(5) adding the solution C into the solution B, violently stirring to obtain a solution D, transferring the solution D into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 160 ℃ for 12 hours to obtain a synthetic product E;
(6) centrifuging and separating the solvent thermal synthesis product E at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product F;
(7) 1G of product F is dissolved in 100 ml of water to give a solution G;
(8) the sample a is immersed in the solution G,ultrasonic deposition is carried out for 6 h, and the carbon cloth loaded BiOCl/BiVO is obtained after deionized water and ethanol washing and drying at 60 ℃ for 3h4The flexible composite photocatalytic material can be recycled.
The obtained carbon cloth loaded BiOCl/BiVO4The method for testing the photocatalytic performance of the recyclable flexible composite photocatalytic material comprises the following steps:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B (Rh B) solution is measured and added with the catalyst. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, taking 4 mL samples from the reaction vessel every 20 min, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst on the pollutant solution according to the absorbance.
Example 10
(1) Cleaning 5 x 5 cm carbon cloth in acetone solution for 30 min to remove impurities such as grease and wax on the surface;
(2) soaking the carbon cloth in concentrated hydrochloric acid solution at room temperature for 10 h;
(3) washing the carbon cloth subjected to acid treatment with water, and drying at 60 ℃ for 6 h to obtain a sample A;
(4) 0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution B; adding 0.4 mmol NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution C;
(5) adding the solution C into the solution B, violently stirring to obtain a solution D, transferring the solution D into a high-pressure autoclave with a polytetrafluoroethylene lining, and keeping the temperature at 200 ℃ for 8 hours to obtain a synthetic product E;
(6) centrifuging and separating the solvent thermal synthesis product E at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product F;
(7) 1.5G of product F was dissolved in 100 ml of water to give solution G;
(8) dipping the sample A in the solution G, carrying out ultrasonic deposition for 6 h, washing with deionized water and ethanol, and drying at 60 ℃ for 3h to obtain the carbon cloth loaded BiOCl/BiVO4The flexible composite photocatalytic material can be recycled.
The obtained carbon cloth loaded BiOCl/BiVO4The method for testing the photocatalytic performance of the recyclable flexible composite photocatalytic material comprises the following steps:
A300W Xe lamp was used as a light source, and a cut-off filter with a wavelength of less than 800 nm was used to simulate sunlight. 50 ml of rhodamine B (Rh B) solution is measured and added with the catalyst. Before illumination, the catalyst and the pollutants are adsorbed and stirred for 30 min in the dark to reach adsorption equilibrium. After turning on the lamp, taking 4 mL samples from the reaction vessel every 20 min, measuring the absorbance of Rh B by using an ultraviolet-visible spectrophotometer, and judging the degradation efficiency of the catalyst on the pollutant solution according to the absorbance.
Referring to FIG. 1, FIG. 1 shows a carbon cloth loaded BiOCl/BiVO4A preparation flow chart and a sample schematic diagram of the recyclable flexible composite photocatalytic material. In the figure: pure carbon cloth is acidified by concentrated hydrochloric acid and then BiVO prepared previously4Carrying out intermediate deposition for a certain time to obtain carbon cloth loaded BiOCl/BiVO4. The sample can be bent and folded at any angle, has excellent flexibility and bendability, does not need to worry about material damage even if being folded for a long time or repeatedly bent, and can be cut according to different use environments.
Referring to FIG. 2, FIG. 2 shows BiVO prepared4And carbon cloth loaded BiOCl/BiVO4The XRD image of the flexible composite photocatalytic material can be recovered. In the figure: a. BiVO prepared at different solvothermal reaction temperatures4It is clearly observed from the XRD patterns of the samples prepared in examples 4, 5, 7 and example 10 that the monoclinic phase BiVO can be generated under the different reaction temperature conditions in the present invention4B, carbon cloth loaded BiOCl/BiVO4XRD (X-ray diffraction) images of recyclable flexible composite photocatalytic materials, and the results in the images can obviously observe that BiOCl and BiVO exist in samples4The characteristic peak of (A) shows that BiVO is deposited after the carbon cloth is acidified4Make part of BiVO4Is converted into BiOCl to successfully generate BiOCl/BiVO4。
The above embodiment shows that the carbon cloth loaded BiOCl/BiVO provided by the invention4Recoverable flexible composite photocatalytic material and its preparationThe preparation method has simple steps, and the prepared carbon cloth loaded BiOCl/BiVO4The recyclable flexible composite photocatalytic material has the advantages of enlarged photoresponse range, improved carrier separation rate, high conductivity, flexibility and bendability, can be randomly cut into required sizes according to actual needs without affecting the performance of the material, and is an effective method and a reliable way for solving the problems of difficult recycling and difficult reutilization of the powder photocatalytic material.
Carbon cloth loaded BiOCl/BiVO4The technology is to solve BiVO4Provides opportunities for band gap problems and carrier recombination problems, using BiVO4And the synergistic effect of the BiOCl and the BiOCl can accelerate the transmission speed of carriers, reduce the recombination rate of photo-generated electron holes, improve the defects of low light absorption, low charge separation rate, poor stability and large energy loss of the BiOCl, reduce the band gap width, enlarge the light absorption range, greatly improve the absorbance and obviously improve the photocatalytic activity, and provide a new idea for the efficient utilization of solar energy and the recycling and reutilization of photocatalysts.
Claims (7)
1. Carbon cloth loaded BiOCl/BiVO4The preparation method of the recyclable flexible composite photocatalytic material is characterized by comprising the following steps:
carbon cloth acidized by concentrated hydrochloric acid is coated on BiVO4Dipping and depositing in the dispersion to obtain the carbon cloth loaded BiOCl/BiVO4The flexible composite photocatalytic material can be recycled.
2. The method according to claim 1, wherein the immersion deposition time is 3 to 15 hours.
3. The method according to claim 1, wherein the acidification time of the carbon cloth in the concentrated hydrochloric acid is 1-10 h.
4. The method of claim 1, wherein BiVO is BiVO4Obtained by a process comprising the steps of: will be dispersed with Bi (NO)3)3And NaVO3The system is subjected to solvothermal reaction for 6-12 h at the temperature of 120-200 ℃ to obtainTo BiVO4。
5. The method of claim 1, comprising the steps of:
1) cleaning 5 x 5 cm carbon cloth in acetone solution for 30 min to remove impurities such as grease and wax on the surface;
2) soaking the carbon cloth in concentrated hydrochloric acid solution at room temperature for 8 h; the soaking time is 1-12 h;
3) washing the carbon cloth subjected to acid treatment with water, and drying at 60 ℃ for 6 h to obtain a sample A;
4) 0.4 mmol of Bi (NO)3)3·5 H2Dissolving O in 16 ml of glycerol to obtain a precursor solution B;
adding 0.4 mmol of NaVO3·2 H2Dissolving O in 16 ml of deionized water to obtain a precursor solution C;
5) adding the solution C into the solution B and stirring vigorously to obtain a solution D; transferring the solution D into a high-pressure autoclave with a polytetrafluoroethylene lining, and carrying out solvothermal reaction for 6-12 h at 120-200 ℃ to obtain a synthetic product E;
6) centrifuging and separating the solvent thermal synthesis product E at 10000 rpm, washing with deionized water and ethanol, and drying at 60 ℃ for 4 hours to obtain a product F;
7) dissolving 0.1-1.5G of the product F in 100 ml of water to obtain a solution G;
8) dipping the sample A in the solution G, carrying out ultrasonic deposition for 3-15 h, washing with deionized water and ethanol, and drying at 60 ℃ for 3h to obtain the carbon cloth loaded BiOCl/BiVO4The flexible composite photocatalytic material can be recycled.
6. Carbon cloth-supported BiOCl/BiVO obtained by the method of any one of claims 1 to 54The flexible composite photocatalytic material can be recycled.
7. Use of the material of claim 6 for photocatalytic degradation of pollutants or photocatalytic oxygen production.
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| CN112495403A (en) * | 2020-12-14 | 2021-03-16 | 陕西科技大学 | BiOCl/Bi2O3Photocatalytic material and preparation method and application thereof |
| CN112830633A (en) * | 2021-01-15 | 2021-05-25 | 上海水生环境工程有限公司 | Method for synergistically purifying conventional and novel pollutants in water |
| CN113457744A (en) * | 2021-07-07 | 2021-10-01 | 齐鲁工业大学 | Silver/copper phthalocyanine/bismuth molybdate flexible photocatalytic material and preparation method and application thereof |
| CN113600216A (en) * | 2021-09-10 | 2021-11-05 | 郑州轻工业大学 | Preparation method of carbon cloth-loaded bismuth phosphate/bismuth oxyhalide flower-shaped photocatalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112495403A (en) * | 2020-12-14 | 2021-03-16 | 陕西科技大学 | BiOCl/Bi2O3Photocatalytic material and preparation method and application thereof |
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| CN113600216A (en) * | 2021-09-10 | 2021-11-05 | 郑州轻工业大学 | Preparation method of carbon cloth-loaded bismuth phosphate/bismuth oxyhalide flower-shaped photocatalyst |
| CN113600216B (en) * | 2021-09-10 | 2023-11-28 | 郑州轻工业大学 | Preparation method of carbon cloth-supported bismuth phosphate/bismuth oxyhalide flower-like photocatalyst |
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