CN109078654A - PVP modified graphene loads BiOCl photochemical catalyst and preparation method thereof - Google Patents
PVP modified graphene loads BiOCl photochemical catalyst and preparation method thereof Download PDFInfo
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- -1 PVP modified graphene Chemical class 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 title abstract 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 58
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 55
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 55
- 239000000243 solution Substances 0.000 claims abstract description 50
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 43
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000001103 potassium chloride Substances 0.000 claims abstract description 8
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 8
- DXOMQVWFKDKKQV-UHFFFAOYSA-N C(CO)O.[N+](=O)([O-])[O-].[Bi+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound C(CO)O.[N+](=O)([O-])[O-].[Bi+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] DXOMQVWFKDKKQV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 41
- 239000011941 photocatalyst Substances 0.000 claims description 38
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 11
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 11
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 8
- 229940012189 methyl orange Drugs 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002135 nanosheet Substances 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 230000000593 degrading effect Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
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- 238000003917 TEM image Methods 0.000 description 7
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- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
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- 239000002064 nanoplatelet Substances 0.000 description 2
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- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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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
- B01J35/39—Photocatalytic properties
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- 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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
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Abstract
A kind of PVP modified graphene load BiOCl photochemical catalyst and preparation method thereof, belongs to photocatalysis technology field.The step are as follows: by bismuth nitrate ethylene glycol solution, potassium chloride and citric acid mixed solution, high pressure mixing reaction, BiOCl is obtained, BiOCl, polyvinylpyrrolidone and graphene solution are mixed, mixed solution is placed in autoclave, under 3~4MPa, it in 140~180 DEG C of 1~5h of reaction, is centrifuged, cleaning, it is dry, obtain PVP modified graphene load BiOCl photochemical catalyst.This method is modified graphene-supported BiOCl as surfactant using polyvinylpyrrolidone, which can inhibit the compound of electron hole pair, changes BiOCl polymerism, improves photocatalysis efficiency.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a PVP modified graphene loaded BiOCl photocatalyst and a preparation method thereof.
Background
The highly developed modern industry is based on fossil energy, and a large amount of harmful waste water, waste gas and waste residue are generated in the process of using the energy, wherein the pollution of the waste water and the waste gas with strong liquidity to the environment is particularly serious. The utilization of solar photocatalytic oxidation technology for pollutant treatment has become a research hotspot. BiOCl is a novel secret oxide photocatalyst. BiOCl is a novel layered semiconductor compound, the crystal structure of which is a tetragonal PbFCl type and can also be regarded as double X along the C axis direction-Layer and [ Bi ]2O2]2+The layered structure formed by the alternate arrangement of the layers belongs to a tetragonal system, the band gap of the layered structure is 3.5ev, and the layered structure is a photocatalyst responding to ultraviolet light. However, the forbidden bandwidth of BiOCl is large, so that the utilization rate of solar energy is low, and the application of BiOCl is limited. Around some factors influencing the performance of the photocatalytic material, the current research work generally adopts the technologies of regulating and controlling the shape and size, depositing noble metals, doping, compounding semiconductor materials, photosensitization and the like to modify the photocatalytic material.
The graphene is formed by a monolayer of carbon atoms passing through sp2The carbon atoms of the hexagonal honeycomb two-dimensional crystal plane structure formed by the hybrid tracks are connected through strong sigma bonds, and the C-C bonds enable the graphene to have excellent structural rigidity and higher strength in the direction parallel to the lamella. The carbon atoms have four valence electrons, so that each carbon atom contributes to an unbonded pi electron, the pi electrons form pi orbitals in the direction vertical to the plane, and the pi electrons move freely in the crystal, so that the graphene has good conductivity. The method for preparing the polyvinylpyrrolidone (PVP) modified graphene loaded BiOCl compound by the two-step hydrothermal method has not been reported.
Disclosure of Invention
The invention solves the key problem of providing PVP modified graphene loaded BiOCl and a preparation method thereof. The polyvinylpyrrolidone is used as a surfactant to modify graphene-loaded BiOCl, and the modified graphene-loaded BiOCl photocatalyst can inhibit the recombination of electron hole pairs, change the BiOCl polymerization phenomenon and improve the photocatalytic efficiency.
The invention discloses a preparation method of PVP modified graphene loaded BiOCl, which comprises the following steps:
step 1: preparing solution
(1) Weighing raw materials according to a ratio, dissolving bismuth nitrate in ethylene glycol, and uniformly stirring to obtain a bismuth nitrate ethylene glycol solution with the molar concentration of 0.1-0.2 mmol/mL;
(2) dissolving potassium chloride and citric acid in a mixed solution of ethanol and water, and uniformly stirring to obtain a mixture A; wherein, according to the mixture ratio, the potassium chloride: citric acid: mixed solution of ethanol and water (3 to 4) mmol: (1-2) mmol: (20-22) mL;
(3) mixing the bismuth nitrate glycol solution with the mixture A to obtain a reaction solution; wherein, according to the mol ratio, Bi is contained in the bismuth nitrate glycol solution3+: cl in mixture A-＝1:1；
Step 2: preparation of BiOCl
(1) Placing the reaction solution in a high-pressure reaction kettle, and reacting at 2-4 MPa and 100-150 ℃ for 10-15 h to obtain a mixture containing BiOCl;
(2) centrifuging the mixture containing BiOCl, cleaning and drying to obtain BiOCl;
and step 3: dispersed graphene solution
(1) Dissolving graphene in a mixed solution of deionized water and absolute ethyl alcohol, and performing ultrasonic dispersion to obtain a graphene solution with the molar concentration of 0.2-0.4 mg/mL;
(2) mixing BiOCl, polyvinylpyrrolidone and graphene solution, and uniformly stirring to obtain a mixed solution B; wherein, according to the mass ratio, the graphene: polyvinylpyrrolidone: 1, BiOCl: (0-60): (15-100);
and 4, step 4: preparation of graphene-loaded BiOCl
(1) Placing the mixed solution B in a high-pressure reaction kettle, and reacting at the temperature of 140-180 ℃ for 1-5 h under the pressure of 3-4 MPa to obtain a mixture containing graphene loaded BiOCl;
(2) and centrifuging, cleaning and drying the mixture containing the graphene-loaded BiOCl to obtain the PVP modified graphene-loaded BiOCl photocatalyst.
Wherein,
in the step 1(2), in the mixed solution of ethanol and water, the volume ratio of ethanol: 1-2% of water.
In the step 2(2), the drying is carried out at a temperature of 70-90 ℃.
In the step 3(1), the ultrasonic dispersion is carried out, and the ultrasonic frequency is 30-50 KHz.
In the step 3(1), in the mixed solution of deionized water and absolute ethyl alcohol, the volume ratio of deionized water: and (1-2) anhydrous ethanol.
In the step 4(2), the drying is carried out at a temperature of 60-90 ℃.
The PVP modified graphene loaded BiOCl photocatalyst is prepared by the preparation method.
The PVP modified graphene loaded BiOCl photocatalyst comprises graphene and BiOCl, wherein BiOCl nanosheets are distributed on the surface of the graphene.
The original appearance of BiOCl is changed by PVP, and BiOCl is attached to the surface of graphene by smaller and irregular nano sheets;
the photocatalytic efficiency of the PVP modified graphene loaded BiOCl photocatalyst for degrading methyl orange in 40min is more than or equal to 98.7%.
The PVP modified graphene loaded BiOCl photocatalyst and the preparation method thereof have the beneficial effects that:
the invention changes the mass ratio of graphene (10mg) to BiOCl, and simultaneously researches the comparison of the effects of adding polyvinylpyrrolidone, wherein the BiOCl is respectively 200mg, 400mg and 600 mg. Those without PVP were designated BR20, BR40, and BR60, and those with PVP were designated BRP20, BRP40, and BRP60, respectively. The method effectively combines the graphene and the BiOCl together, improves the photocatalysis effect, and has the degradation rate as high as 98.7% after 40 min; the preparation process is simple, the cost is low, the time consumption is low, and the rapid production can be realized.
Drawings
FIG. 1 is an XRD pattern of a PVP modified graphene supported BiOCl photocatalyst in examples 1-6 of the present invention;
FIG. 2 is a TEM image of BiOCl prepared in example 1 of the present invention;
FIG. 3 is a TEM image of BR20 prepared in example 4 of the present invention;
FIG. 4 is a TEM image of BRP20 prepared in example 1 of the present invention;
FIG. 5 is a graph of the degradation rate of a PVP modified graphene loaded BiOCl photocatalyst in examples 1-6 of the present invention;
fig. 6 is a schematic flow chart of a preparation method of the PVP-modified graphene-supported BiOCl photocatalyst of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
A preparation method of PVP modified graphene loaded BiOCl is shown in a schematic flow diagram of FIG. 6, and comprises the following steps:
step 1: preparing solution
(1) Dissolving 3mmol of bismuth nitrate in 20mL of ethylene glycol, and uniformly stirring to obtain a bismuth nitrate ethylene glycol solution with the molar concentration of 0.15 mmol/mL;
(2) dissolving 3mmol of potassium chloride and 1mmol of citric acid in a mixed solution of 7mL of ethanol and 14mL of water, and uniformly stirring to obtain a mixture A;
(3) mixing the bismuth nitrate glycol solution with the mixture A to obtain a reaction solution;
step 2: preparation of BiOCl
(1) Placing the reaction solution in a high-pressure reaction kettle, and reacting at 150 ℃ for 10h under 4MPa to obtain a mixture containing BiOCl;
(2) centrifuging the mixture containing BiOCl, washing with deionized water and absolute ethyl alcohol for several times, and drying at 80 ℃ to obtain BiOCl;
the obtained BiOCl is analyzed, an obtained TEM image is shown in figure 2, and the obtained TEM image is shown in figure 2, wherein the size of the BiOCl nanosheet is 60-150 nm multiplied by 50-70 nm, and the thickness of the BiOCl nanosheet is 10-20 nm.
And step 3: dispersed graphene solution
(1) Dissolving 10mg of graphene in a mixed solution of 15mL of deionized water and 10mL of absolute ethyl alcohol, and performing ultrasonic dispersion to obtain a graphene solution with a molar concentration of 0.4 mg/mL;
(2) mixing 200mg of BiOCl, 15mg of polyvinylpyrrolidone and graphene solution, and uniformly stirring to obtain a mixed solution B;
and 4, step 4: preparation of graphene-loaded BiOCl
(1) Placing the mixed solution B in a high-pressure reaction kettle, and reacting at 180 ℃ for 1h under 3MPa to obtain a mixture containing graphene-loaded BiOCl;
(2) centrifuging the mixture containing the graphene-loaded BiOCl, washing the mixture with deionized water and absolute ethyl alcohol for several times, and drying the mixture at 60 ℃ to obtain the PVP-modified graphene-loaded BiOCl photocatalyst, wherein the PVP-modified graphene-loaded BiOCl photocatalyst prepared in the embodiment is BRP20 according to the addition of 200mg of BiOCl and 15mg of polyvinylpyrrolidone in the step 3.
Test analysis of BRP20 prepared in this example gave a TEM image of BRP20 shown in FIG. 4, from which it can be seen that the amount of BiOCl nanoplatelets on the surface of the RGO (graphene) layer increases significantly and the size of the BiOCl nanoplatelets decreases. The result shows that the appearance of the BiOCl nanosheet can be changed by adding PVP, and the agglomeration of the BiOCl nanosheet is inhibited.
Example 2
The preparation method of the PVP modified graphene loaded BiOCl is the same as that in example 1, except that:
(1) in step 3, 400mg of BiOCl and 15mg of polyvinylpyrrolidone are added, and the PVP-modified graphene-supported BiOCl photocatalyst prepared in this embodiment is BRP 40.
Example 3
The preparation method of the PVP modified graphene loaded BiOCl is the same as that in example 1, except that:
(1) in step 3, 600mg of BiOCl and 15mg of polyvinylpyrrolidone are added, and the PVP-modified graphene-supported BiOCl photocatalyst prepared in this embodiment is BRP 40.
Example 4
A preparation method of graphene-loaded BiOCl, which is the same as example 1 except that:
(1) in step 3, 200mg of BiOCl is added, and polyvinylpyrrolidone is not added, so that the graphene-supported BiOCl photocatalyst prepared in this embodiment is BR 20.
Analysis of BR20 prepared in this example showed that BR20 in the TEM image of FIG. 3 and BR20 showed a good ordered structure, as can be seen from FIG. 3, indicating that RGO favors crystal growth.
Example 5
A preparation method of graphene-loaded BiOCl, which is the same as example 1 except that:
(1) in step 3, 400mg of BiOCl is added, and polyvinylpyrrolidone is not added, so that the graphene-supported BiOCl photocatalyst prepared in this embodiment is BR 40.
Example 6
A preparation method of graphene-loaded BiOCl, which is the same as example 1 except that:
(1) in step 3, 600mg of BiOCl is added, and polyvinylpyrrolidone is not added, so that the graphene-supported BiOCl photocatalyst prepared in this embodiment is BR 60.
XRD analysis is carried out on the graphene-loaded BiOCl photocatalyst prepared in the embodiments 1-6 and the raw material BiOCl, an obtained XRD pattern is shown in figure 1, the XRD pattern can be obtained from figure 1, and the images of the graphene-loaded BiOCl photocatalyst prepared in the embodiments 1-6 are completely consistent with that of a tetragonal phase BiOCl shown in figure 1. The prepared graphene-loaded BiOCl photocatalyst has no obvious diffraction peak of other impurities, which indicates that the purity of the prepared product is very high. The diffraction peaks for all samples were substantially the same, so the addition of graphene did not change the crystalline phase of the material.
The degradation rate of the graphene-supported BiOCl photocatalyst prepared in the embodiments 1-6 is analyzed, and the result is shown in FIG. 5, wherein BRP60 shows the highest photocatalytic performance in BiOCl series composite materials, and the catalytic effect reaches 98.7%.
Example 7
A preparation method of PVP modified graphene loaded BiOCl comprises the following steps:
step 1, solution preparation
(1) Dissolving 2mmol of bismuth nitrate in a beaker 1 filled with 20mL of ethylene glycol solution, and uniformly stirring to obtain bismuth nitrate ethylene glycol solution with the molar concentration of 0.1 mmol/mL;
(2) dissolving 4mmol of potassium chloride and 2mmol of citric acid in a beaker 2 filled with 11mL of ethanol and 11mL of deionized water, and uniformly stirring to obtain a mixture A;
(3) slowly pouring the mixture A solution in the beaker 2 into the bismuth nitrate ethylene glycol solution in the beaker 1 at a constant speed, and uniformly stirring to obtain a reaction solution;
step 2, preparation of BiOCl
And pouring the mixed reaction solution into a high-pressure reaction kettle, and heating for 15 hours at 100 ℃ under 3MPa to obtain a mixture containing BiOCl.
(2) The mixture containing BiOCl was centrifuged, washed several times with deionized water and absolute ethanol, and dried at 70 ℃ to give BiOCl.
Step 3, dispersing the graphene solution
(1) Dissolving 20mg of graphene in 40mL of deionized water and 20mL of absolute ethyl alcohol, and carrying out ultrasonic treatment for 30-40 min to make the graphene uniform, so as to obtain a graphene solution with the molar concentration of 0.33 mg/mL;
(2) mixing 300mgBiOCl, 15mg polyvinylpyrrolidone and graphene solution, and stirring for 2-3 h to obtain a uniform mixed solution B.
Step 4, preparing graphene-loaded BiOCl
(1) And pouring the mixed solution B into a high-pressure reaction kettle, and heating for 5 hours at 140 ℃ to obtain a mixture containing graphene-loaded BiOCl.
(2) And centrifuging the mixture containing the graphene-loaded BiOCl, washing the mixture for a plurality of times by using deionized water and absolute ethyl alcohol, and drying the mixture at the temperature of 60-90 ℃ to obtain the PVP modified graphene-loaded BiOCl photocatalyst.
Step 5, photocatalytic experiment
The prepared photocatalyst (30mg) was dispersed in 50mL of a methyl orange aqueous solution at a concentration of 20mg/L, and the suspension was magnetically stirred in the dark for 30 minutes before light irradiation to achieve adsorption/desorption equilibrium between the photocatalyst and methyl orange. Then, 4mL of suspension was taken every 10 minutes during irradiation and centrifuged. The solution centrifuged at the wavelength of maximum absorption was recorded.
The photocatalytic efficiency of the PVP modified graphene supported BiOCl photocatalyst prepared in the embodiment for degrading methyl orange within 40min is 98.9%.
Example 8
A preparation method of PVP modified graphene loaded BiOCl comprises the following steps:
step 1, solution preparation
(1) Dissolving 3mmol of bismuth nitrate in a beaker 1 filled with 20mL of glycol solution, and magnetically stirring for 30min to obtain bismuth nitrate glycol solution with the molar concentration of 0.1 mmol/mL;
(2) dissolving 3mmol of potassium chloride and 1mmol of citric acid in a beaker 2 containing 10mL of ethanol and 10mL of deionized water; stirring for 30min by magnetic force, and stirring uniformly to obtain a mixture A;
(3) slowly pouring the mixture A solution in the beaker 2 into the bismuth nitrate ethylene glycol solution in the beaker 1 at a constant speed, and magnetically stirring for 30min to obtain a reaction solution;
step 2, preparing BiOCl with high specific surface area
And pouring the mixed reaction solution into a high-pressure reaction kettle, and heating at 120 ℃ for 12h under 3MPa to obtain a mixture containing BiOCl.
(2) And centrifuging the mixture containing BiOCl, washing the BiOCl with high specific surface area for several times by using deionized water and absolute ethyl alcohol, and drying at 80 ℃ to obtain the BiOCl.
Step 3, dispersing the graphene solution
(1) Dissolving 10mg of graphene in 20mL of deionized water and 10mL of absolute ethyl alcohol, and carrying out ultrasonic treatment for 30min to obtain a graphene solution with the molar concentration of 0.33 mg/mL;
(2) 200mg of BiOCl and 10mg of polyvinylpyrrolidone are mixed with the graphene solution, and the mixture is magnetically stirred for 2 hours to obtain a mixed solution B.
Step 4, preparing graphene-loaded BiOCl
(1) And pouring the mixed solution B into a high-pressure reaction kettle, and heating at 160 ℃ for 3h to obtain a mixture containing graphene-loaded BiOCl.
(2) And centrifuging the mixture containing the graphene-loaded BiOCl, washing the mixture for several times by using deionized water and absolute ethyl alcohol, and drying the mixture at 80 ℃ to obtain the PVP modified graphene-loaded BiOCl photocatalyst.
Step 5, photocatalytic experiment
The prepared photocatalyst (30mg) was dispersed in 50mL of a methyl orange aqueous solution at a concentration of 20mg/L, and the suspension was magnetically stirred in the dark for 30 minutes before light irradiation to achieve adsorption/desorption equilibrium between the photocatalyst and methyl orange. Then, 4mL of suspension was taken every 10 minutes during irradiation and centrifuged. The solution centrifuged at the wavelength of maximum absorption was recorded.
The photocatalytic efficiency of the PVP modified graphene supported BiOCl photocatalyst prepared in the embodiment for degrading methyl orange within 40min is 98.7%.
Claims (9)
1. A preparation method of PVP modified graphene loaded BiOCl is characterized by comprising the following steps:
step 1: preparing solution
(1) Weighing raw materials according to a ratio, dissolving bismuth nitrate in ethylene glycol, and uniformly stirring to obtain a bismuth nitrate ethylene glycol solution with the molar concentration of 0.1-0.2 mmol/mL;
(2) dissolving potassium chloride and citric acid in a mixed solution of ethanol and water, and uniformly stirring to obtain a mixture A; wherein, according to the mixture ratio, the potassium chloride: citric acid: mixed solution of ethanol and water (3 to 4) mmol: (1-2) mmol: (20-22) mL;
(3) mixing the bismuth nitrate glycol solution with the mixture A to obtain a reaction solution; wherein, according to the mol ratio, Bi is contained in the bismuth nitrate glycol solution3+: cl in mixture A-＝1:1；
Step 2: preparation of BiOCl
(1) Placing the reaction solution in a high-pressure reaction kettle, and reacting at 2-4 MPa and 100-150 ℃ for 10-15 h to obtain a mixture containing BiOCl;
(2) centrifuging the mixture containing BiOCl, cleaning and drying to obtain BiOCl;
and step 3: dispersed graphene solution
(1) Dissolving graphene in a mixed solution of deionized water and absolute ethyl alcohol, and performing ultrasonic dispersion to obtain a graphene solution with the molar concentration of 0.2-0.4 mg/mL;
(2) mixing BiOCl, polyvinylpyrrolidone and graphene solution, and uniformly stirring to obtain a mixed solution B; wherein, according to the mass ratio, the graphene: polyvinylpyrrolidone: 1, BiOCl: (0-60): (15-100);
and 4, step 4: preparation of graphene-loaded BiOCl
(1) Placing the mixed solution B in a high-pressure reaction kettle, and reacting at the temperature of 140-180 ℃ for 1-5 h under the pressure of 3-4 MPa to obtain a mixture containing graphene loaded BiOCl;
(2) and centrifuging, cleaning and drying the mixture containing the graphene-loaded BiOCl to obtain the PVP modified graphene-loaded BiOCl photocatalyst.
2. The method for preparing PVP-modified graphene-supported BiOCl according to claim 1, wherein in the step 1(2), in a mixed solution of ethanol and water, the ratio of ethanol: 1-2% of water.
3. The method for preparing PVP modified graphene loaded BiOCl according to claim 1, wherein in the step 2(2), the drying temperature is 70-90 ℃.
4. The method for preparing PVP modified graphene loaded BiOCl according to claim 1, wherein in the step 3(1), the ultrasonic dispersion is performed, and the ultrasonic frequency is 30-50 KHz.
5. The method for preparing the PVP-modified graphene-supported BiOCl according to claim 1, wherein in the step 3(1), in a mixed solution of deionized water and absolute ethyl alcohol, the volume ratio of deionized water: and (1-2) anhydrous ethanol.
6. The method for preparing PVP modified graphene loaded BiOCl according to claim 1, wherein in the step 4(2), the drying temperature is 60-90 ℃.
7. A PVP modified graphene supported BiOCl photocatalyst is prepared by the preparation method of the PVP modified graphene supported BiOCl photocatalyst in claim 1.
8. The PVP modified graphene loaded BiOCl photocatalyst is characterized by comprising graphene and BiOCl, wherein BiOCl nanosheets are distributed on the surface of the graphene.
9. The PVP modified graphene-supported BiOCl photocatalyst of claim 7 or 8, wherein the photocatalytic efficiency of the PVP modified graphene-supported BiOCl photocatalyst in degrading methyl orange within 40min is greater than or equal to 98.7%.
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