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
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- -1 PVP modified graphene Chemical class 0.000 title claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 61
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 60
- 239000000243 solution Substances 0.000 claims abstract description 52
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 46
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 37
- 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
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 16
- 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 11
- 230000001699 photocatalysis Effects 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000007146 photocatalysis Methods 0.000 claims abstract description 10
- 239000001103 potassium chloride Substances 0.000 claims abstract description 8
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- 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
- 238000003756 stirring Methods 0.000 claims description 8
- 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 7
- 229960004756 ethanol Drugs 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000013078 crystal Chemical group 0.000 description 6
- 238000013019 agitation Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 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 2
- 230000000694 effects Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
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Classifications
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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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B01J35/39—
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
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 photocatalysis technology fields, and in particular to a kind of PVP modified graphene load BiOCl photochemical catalyst and
Preparation method.
Background technique
Highly developed modern industry is built upon on the basis of fossil energy, is generated during using these energy
A large amount of harmful waste water,wastes gas and industrial residue, wherein more liquid waste water and exhaust gas is especially serious to the pollution of environment.Benefit
Pollutant control, which is carried out, with solar photocatalytic oxidation technology has become research hotspot.BiOCl is a kind of novel secret base oxidation
Object light catalyst.BiOCl is a kind of novel lamellar semiconducting compound, and crystal structure is that four directions PbFCl type can also be regarded as along C axis
Double X in direction-Layer and [Bi2O2]2+Layer is alternately arranged the layer structure of composition, belongs to tetragonal crystal system, and band gap therein is 3.5ev,
It is the photochemical catalyst of ultraviolet light response.However the forbidden bandwidth of BiOCl is larger, causes the utilization rate to solar energy low, limits
The application of BiOCl.Around some factors for influencing catalysis material performance, current research work is often using regulation pattern ruler
Very little, noble metal loading, doping, semiconductor material be compound and the technologies such as photosensitizer are modified catalysis material.
Graphene is to pass through sp by single layer of carbon atom2The hexagon cellular shape two dimensional crystal planar structure of hybridized orbit composition,
It is connected between carbon atom by very strong σ key, these C-C keys make graphene have excellent structural rigidity, parallel sheet direction
Intensity is higher.For carbon atom there are four valence electron, carbon atom each in this way contributes a non-bonding pi-electron, these pi-electrons with
The vertical direction of plane forms π track, and pi-electron moves freely in crystal, and graphene is made to have good electric conductivity.The present invention
Method, two one-step hydrothermals prepare polyvinylpyrrolidone (PVP) modified graphene load BiOCl compound have not been reported.
Summary of the invention
It is that the present invention solves it is a key issue that providing a kind of PVP modified graphene load BiOCl and preparation method thereof.It is poly-
Vinylpyrrolidone is modified graphene-supported BiOCl as surfactant, the modified graphene-supported BiOCl
Photochemical catalyst can inhibit the compound of electron hole pair, change BiOCl polymerism, improve photocatalysis efficiency.
The preparation method of PVP modified graphene load BiOCl of the invention a kind of, comprising the following steps:
Step 1: preparing solution
(1) according to the ratio, weigh raw material, bismuth nitrate is dissolved in ethylene glycol, is stirred evenly, obtain molar concentration be 0.1~
In the bismuth nitrate ethylene glycol solution of 0.2mmol/mL；
(2) potassium chloride and citric acid are dissolved in the mixed liquor of second alcohol and water, are stirred evenly, obtain mixture A；Wherein,
According to the ratio, potassium chloride: citric acid: the mixed liquor of second alcohol and water=(3~4) mmol:(1~2) mmol:(20~22) mL；
(3) bismuth nitrate ethylene glycol solution and mixture A are mixed, obtains reaction solution；Wherein, in molar ratio, bismuth nitrate
Bi in ethylene glycol solution3+: Cl in mixture A-=1:1；
Step 2: preparation BiOCl
(1) reaction solution is placed in autoclave, is obtained in 2~4MPa in 100~150 DEG C of 10~15h of reaction
Mixture containing BiOCl；
(2) mixture containing BiOCl is centrifuged, is cleaned and dried, obtains BiOCl；
Step 3: dispersed graphite alkene solution
(1) graphene is dissolved in the mixed liquor of deionized water and dehydrated alcohol, ultrasonic disperse, obtaining molar concentration is
The graphene solution of 0.2~0.4mg/mL；
(2) BiOCl, polyvinylpyrrolidone and graphene solution are mixed, stirs evenly, obtains mixed solution B；Its
In, in mass ratio, graphene: polyvinylpyrrolidone: BiOCl=1:(0~60): (15~100)；
Step 4: preparing graphene-supported BiOCl
(1) mixed solution B is placed in autoclave, under 3~4MPa, in 140~180 DEG C of 1~5h of reaction, is contained
The mixture of graphene-supported BiOCl；
(2) mixture of containing graphene load BiOCl is centrifuged, is cleaned, it is dry, obtain the load of PVP modified graphene
BiOCl photochemical catalyst.
Wherein,
In the step 1 (2), in the mixed liquor of second alcohol and water, by volume, ethyl alcohol: water=1:(1~2).
In the step 2 (2), the drying, drying temperature is 70~90 DEG C.
In the step 3 (1), the ultrasonic disperse, supersonic frequency is 30~50KHz.
In the step 3 (1), in the mixed liquor of deionized water and dehydrated alcohol, by volume, deionized water: anhydrous
Ethyl alcohol=2:(1~2).
In the step 4 (2), the drying, drying temperature is 60~90 DEG C.
A kind of PVP modified graphene of the invention loads BiOCl photochemical catalyst, is made by above-mentioned preparation method.
The PVP modified graphene loads BiOCl photochemical catalyst, including graphene and BiOCl, BiOCl nanometer sheet point
Cloth is on the surface of graphene.
The BiOCl changes original pattern by PVP, and BiOCl is attached to stone with smaller, random nanometer sheet
Black alkene surface；
The described PVP modified graphene load BiOCl photochemical catalyst degrade in 40min the photocatalysis efficiency of methyl orange >=
98.7%.
PVP modified graphene load BiOCl photochemical catalyst of the invention and preparation method thereof, it has the advantage that:
The present invention changes graphene (10mg) and BiOCl mass ratio, while probing into and polyvinylpyrrolidone effect pair is added
Than BiOCl is respectively 200mg, 400mg, 600mg.PVP is not added is denoted as BR20, BR40, BR60 respectively, and the difference of PVP is added
It is denoted as BRP20, BRP40 and BRP60.Graphene and BiOCl are effectively combined together by this method, improve photocatalysis effect
Fruit, degradation rate is up to 98.7% after 40min；Preparation process is simple, at low cost, and time-consuming is few, can quickly produce.
Detailed description of the invention
Fig. 1 is the XRD diagram that 1-6PVP of embodiment of the present invention modified graphene loads BiOCl photochemical catalyst；
The TEM figure that Fig. 2 is BiOCl prepared by the embodiment of the present invention 1；
The TEM figure that Fig. 3 is BR20 prepared by the embodiment of the present invention 4；
The TEM figure that Fig. 4 is BRP20 prepared by the embodiment of the present invention 1；
Fig. 5 is the degradation rate figure that 1-6PVP of embodiment of the present invention modified graphene loads BiOCl photochemical catalyst；
Fig. 6 is the flow diagram for the preparation method that PVP modified graphene of the present invention loads BiOCl photochemical catalyst.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail.
Embodiment 1
A kind of preparation method of PVP modified graphene load BiOCl, flow diagram are shown in Fig. 6, comprising the following steps:
Step 1: preparing solution
(1) 3mmol bismuth nitrate is dissolved in 20mL ethylene glycol, is stirred evenly, obtaining molar concentration is 0.15mmol/mL's
In bismuth nitrate ethylene glycol solution；
(2) 3mmol potassium chloride and 1mmol citric acid are dissolved in the mixed liquor of 7mL ethyl alcohol and 14mL water, are stirred evenly,
Obtain mixture A；
(3) bismuth nitrate ethylene glycol solution and mixture A are mixed, obtains reaction solution；
Step 2: preparation BiOCl
(1) reaction solution is placed in autoclave, obtains the mixing containing BiOCl in 150 DEG C of reaction 10h in 4MPa
Object；
(2) mixture containing BiOCl is centrifuged, several times with deionized water and washes of absolute alcohol, in 80 DEG C of dryings, is obtained
To BiOCl；
BiOCl obtained to be analyzed, obtained TEM figure is shown in Fig. 2, as can be drawn from Figure 2, BiOCl nanometer sheet ruler
Very little is 60~150nm × 50~70nm, with a thickness of 10~20nm.
Step 3: dispersed graphite alkene solution
(1) 10mg graphene is dissolved in the mixed liquor of 15mL deionized water and 10mL dehydrated alcohol, ultrasonic disperse obtains
Molar concentration is the graphene solution of 0.4mg/mL；
(2) BiOCl, 15mg polyvinylpyrrolidone and graphene solution of 200mg are mixed, stirs evenly, is mixed
Close solution B；
Step 4: preparing graphene-supported BiOCl
(1) mixed solution B is placed in autoclave, under 3MPa, in 180 DEG C of reaction 1h, obtains containing graphene load
The mixture of BiOCl；
(2) mixture of containing graphene load BiOCl is centrifuged, several times with deionized water and washes of absolute alcohol, 60
DEG C drying obtains PVP modified graphene load BiOCl photochemical catalyst, according in step 3, BiOCl, 15mg of the 200mg of addition
The load BiOCl photochemical catalyst of PVP modified graphene made from the present embodiment is BRP20 by polyvinylpyrrolidone.
Test analysis is carried out to BRP20 manufactured in the present embodiment, the TEM figure of obtained BRP20 is shown in Fig. 4, can be with from Fig. 4
Find out, the significant increase of amount of the BiOCl nanometer sheet in RGO (graphene) layer surface, and the size of BiOCl nanometer sheet reduces.
The result shows that addition PVP can change the pattern of BiOCl nanometer sheet, inhibit the reunion of BiOCl nanometer sheet.
Embodiment 2
A kind of preparation method of PVP modified graphene load BiOCl, with embodiment 1, the difference is that:
(1) in step 3, BiOCl, 15mg polyvinylpyrrolidone of the 400mg of addition, by PVP made from the present embodiment
It is BRP40 that modified graphene, which loads BiOCl photochemical catalyst,.
Embodiment 3
A kind of preparation method of PVP modified graphene load BiOCl, with embodiment 1, the difference is that:
(1) in step 3, BiOCl, 15mg polyvinylpyrrolidone of the 600mg of addition, by PVP made from the present embodiment
It is BRP40 that modified graphene, which loads BiOCl photochemical catalyst,.
Embodiment 4
A kind of preparation method of graphene-supported BiOCl, with embodiment 1, the difference is that:
(1) in step 3, polyvinylpyrrolidone is not added by the BiOCl of the 200mg of addition, by stone made from the present embodiment
Black alkene load BiOCl photochemical catalyst is BR20.
BR20 manufactured in the present embodiment is analyzed, the TEM figure of BR20 is shown in Fig. 3, as can be drawn from Figure 3, BR20
It shows good ordered structure, shows that RGO is conducive to the growth of crystal.
Embodiment 5
A kind of preparation method of graphene-supported BiOCl, with embodiment 1, the difference is that:
(1) in step 3, polyvinylpyrrolidone is not added by the BiOCl of the 400mg of addition, by stone made from the present embodiment
Black alkene load BiOCl photochemical catalyst is BR40.
Embodiment 6
A kind of preparation method of graphene-supported BiOCl, with embodiment 1, the difference is that:
(1) in step 3, polyvinylpyrrolidone is not added by the BiOCl of the 600mg of addition, by stone made from the present embodiment
Black alkene load BiOCl photochemical catalyst is BR60.
XRD analysis is carried out to the graphene-supported BiOCl photochemical catalyst and raw material BiOCl of Examples 1 to 6 preparation, is obtained
To XRD diagram see Fig. 1, it is available from Fig. 1, Examples 1 to 6 preparation graphene-supported BiOCl photochemical catalyst image with
Tetragonal phase BiOCl in Fig. 1 is completely the same.There is no the obvious of other impurities in the graphene-supported BiOCl photochemical catalyst of preparation
Diffraction maximum shows that the purity of prepared product is very high.The diffraction maximum of all samples is essentially identical, therefore adding graphene will not
Change the crystal phase of material.
The degradation rate of the graphene-supported BiOCl photochemical catalyst of Examples 1 to 6 preparation is analyzed, the result is shown in figures
5, wherein BRP60 shows highest photocatalysis performance in BiOCl series composite materials, and catalytic effect reaches 98.7%.
Embodiment 7
A kind of preparation method of PVP modified graphene load BiOCl, comprising the following steps:
Step 1, prepared by solution
(1) 2mmol bismuth nitrate is dissolved in equipped in 20ml ethylene glycol solution beaker 1, is stirred evenly, obtaining molar concentration is
The bismuth nitrate ethylene glycol solution of 0.1mmol/mL；
(2) 4mmol potassium chloride and 2mmol citric acid are dissolved in equipped in 11mL ethyl alcohol and 11mL deionized water beaker 2, are stirred
It mixes uniformly, obtains mixture A；
(3) the mixture solution A uniform speed slow in beaker 2 is poured into the bismuth nitrate ethylene glycol solution of beaker 1, stirring is equal
It is even, obtain reaction solution；
Step 2, BiOCl is prepared
Mixed reaction solution is poured into autoclave, is obtained in 3MPa, 100 DEG C of heating 15h containing BiOCl's
Mixture.
(2) mixture containing BiOCl is centrifuged, several times with deionized water and washes of absolute alcohol BiOCl, at 70 DEG C
It is dry, obtain BiOCl.
Step 3, dispersed graphite alkene solution
(1) 20mg graphene is dissolved in 40mL deionized water and 20mL dehydrated alcohol, 30~40min of ultrasound, makes it
It is even, obtain the graphene solution that molar concentration is 0.33mg/mL；
(2) 300mgBiOCl, 15mg polyvinylpyrrolidone, graphene solution three are mixed, stirs 2~3h, makes it
Uniformly, mixed solution B is obtained.
Step 4, graphene-supported BiOCl is prepared
(1) mixed solution B is poured into autoclave, 140 DEG C of heating 5h, obtains the mixed of containing graphene load BiOCl
Close object.
(2) mixture of containing graphene load BiOCl is centrifuged, several times with deionized water and washes of absolute alcohol,
It is dry at 60~90 DEG C, obtain PVP modified graphene load BiOCl photochemical catalyst.
Step 5, photocatalysis is tested
The photochemical catalyst prepared (30mg) is dispersed in the 50mL methyl orange aqueous solution that concentration is 20mg/L, in illumination
Before penetrating, by suspension magnetic agitation 30 minutes in the dark, to realize that the adsorption/desorption between photochemical catalyst and methyl orange is flat
Weighing apparatus.Then, it takes 4mL suspension and is centrifuged within every 10 minutes during irradiation.Record the solution of maximum absorption wavelength centrifugation.
Degrade in the 40min light of methyl orange of PVP modified graphene manufactured in the present embodiment load BiOCl photochemical catalyst is urged
Changing efficiency is 98.9%.
Embodiment 8
A kind of preparation method of PVP modified graphene load BiOCl, comprising the following steps:
Step 1, prepared by solution
(1) 3mmol bismuth nitrate is dissolved in equipped in 20mL ethylene glycol solution beaker 1, magnetic agitation 30min, is obtained mole
Concentration is the bismuth nitrate ethylene glycol solution of 0.1mmol/mL；
(2) 3mmol potassium chloride and 1mmol citric acid are dissolved in equipped in 10mL ethyl alcohol and 10mL deionized water beaker 2；Magnetic
Power stirs 30min, stirs evenly, obtains mixture A；
(3) the mixture solution A uniform speed slow in beaker 2 is poured into the bismuth nitrate ethylene glycol solution of beaker 1, magnetic force stirs
30min is mixed, reaction solution is obtained；
Step 2, high-specific surface area BiOCl is prepared
Mixed reaction solution is poured into autoclave, is obtained in 3MPa, 120 DEG C of heating 12h containing BiOCl's
Mixture.
(2) mixture containing BiOCl is centrifuged, it is several with deionized water and washes of absolute alcohol high-specific surface area BiOCl
It is secondary, it is dry at 80 DEG C, obtain BiOCl.
Step 3, dispersed graphite alkene solution
(1) 10mg graphene is dissolved in 20mL deionized water and 10mL dehydrated alcohol, ultrasonic 30min, is obtained mole dense
Degree is the graphene solution of 0.33mg/mL；
(2) 200mgBiOCl and 10mg polyvinylpyrrolidone is mixed with graphene solution, magnetic agitation 2h is mixed
Close solution B.
Step 4, graphene-supported BiOCl is prepared
(1) mixed solution B is poured into autoclave, 160 DEG C of heating 3h, obtains the mixed of containing graphene load BiOCl
Close object.
(2) mixture of containing graphene load BiOCl is centrifuged, several times with deionized water and washes of absolute alcohol,
It is dry at 80 DEG C, obtain PVP modified graphene load BiOCl photochemical catalyst.
Step 5, photocatalysis is tested
The photochemical catalyst prepared (30mg) is dispersed in the 50mL methyl orange aqueous solution that concentration is 20mg/L, in illumination
Before penetrating, by suspension magnetic agitation 30 minutes in the dark, to realize that the adsorption/desorption between photochemical catalyst and methyl orange is flat
Weighing apparatus.Then, it takes 4mL suspension and is centrifuged within every 10 minutes during irradiation.Record the solution of maximum absorption wavelength centrifugation.
Degrade in the 40min light of methyl orange of PVP modified graphene manufactured in the present embodiment load BiOCl photochemical catalyst is urged
Changing efficiency is 98.7%.
Claims (9)
1. a kind of preparation method of PVP modified graphene load BiOCl, which comprises the following steps:
Step 1: preparing solution
(1) according to the ratio, weigh raw material, bismuth nitrate is dissolved in ethylene glycol, is stirred evenly, obtain molar concentration be 0.1~
In the bismuth nitrate ethylene glycol solution of 0.2mmol/mL；
(2) potassium chloride and citric acid are dissolved in the mixed liquor of second alcohol and water, are stirred evenly, obtain mixture A；Wherein, by matching
Than potassium chloride: citric acid: the mixed liquor of second alcohol and water=(3~4) mmol:(1~2) mmol:(20~22) mL；
(3) bismuth nitrate ethylene glycol solution and mixture A are mixed, obtains reaction solution；Wherein, in molar ratio, bismuth nitrate second two
Bi in alcoholic solution3+: Cl in mixture A-=1:1；
Step 2: preparation BiOCl
(1) reaction solution is placed in autoclave, is contained in 2~4MPa in 100~150 DEG C of 10~15h of reaction
The mixture of BiOCl；
(2) mixture containing BiOCl is centrifuged, is cleaned and dried, obtains BiOCl；
Step 3: dispersed graphite alkene solution
(1) graphene is dissolved in the mixed liquor of deionized water and dehydrated alcohol, ultrasonic disperse, obtain molar concentration be 0.2~
The graphene solution of 0.4mg/mL；
(2) BiOCl, polyvinylpyrrolidone and graphene solution are mixed, stirs evenly, obtains mixed solution B；Wherein, it presses
Mass ratio, graphene: polyvinylpyrrolidone: BiOCl=1:(0~60): (15~100)；
Step 4: preparing graphene-supported BiOCl
(1) mixed solution B is placed in autoclave, under 3~4MPa, in 140~180 DEG C of 1~5h of reaction, obtains graphitiferous
The mixture of alkene load BiOCl；
(2) mixture of containing graphene load BiOCl is centrifuged, is cleaned, it is dry, obtain PVP modified graphene load BiOCl light
Catalyst.
2. the preparation method of PVP modified graphene load BiOCl as described in claim 1, which is characterized in that the step
In 1 (2), in the mixed liquor of second alcohol and water, by volume, ethyl alcohol: water=1:(1~2).
3. the preparation method of PVP modified graphene load BiOCl as described in claim 1, which is characterized in that the step
In 2 (2), the drying, drying temperature is 70~90 DEG C.
4. the preparation method of PVP modified graphene load BiOCl as described in claim 1, which is characterized in that the step
In 3 (1), the ultrasonic disperse, supersonic frequency is 30~50KHz.
5. the preparation method of PVP modified graphene load BiOCl as described in claim 1, which is characterized in that the step
In 3 (1), in the mixed liquor of deionized water and dehydrated alcohol, by volume, deionized water: dehydrated alcohol=2:(1~2).
6. the preparation method of PVP modified graphene load BiOCl as described in claim 1, which is characterized in that the step
In 4 (2), the drying, drying temperature is 60~90 DEG C.
7. a kind of PVP modified graphene loads BiOCl photochemical catalyst, loaded using PVP modified graphene described in claim 1
The preparation method of BiOCl is made.
8. a kind of PVP modified graphene loads BiOCl photochemical catalyst, which is characterized in that the PVP modified graphene loads BiOCl
Photochemical catalyst includes graphene and BiOCl, and BiOCl nanometer sheet is distributed on the surface of graphene.
9. PVP modified graphene as claimed in claim 7 or 8 loads BiOCl photochemical catalyst, which is characterized in that the PVP
Modified graphene load BiOCl photochemical catalyst is degraded photocatalysis efficiency >=98.7% of methyl orange in 40min.
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