CN106824271B - A kind of PVDF-Ag/AgBr/g-C3N4The preparation method of-BiOCl (001) composite membrane - Google Patents
A kind of PVDF-Ag/AgBr/g-C3N4The preparation method of-BiOCl (001) composite membrane Download PDFInfo
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- CN106824271B CN106824271B CN201710119934.0A CN201710119934A CN106824271B CN 106824271 B CN106824271 B CN 106824271B CN 201710119934 A CN201710119934 A CN 201710119934A CN 106824271 B CN106824271 B CN 106824271B
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- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 title claims abstract description 149
- 238000002360 preparation method Methods 0.000 title claims abstract description 120
- 239000012528 membrane Substances 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000002033 PVDF binder Substances 0.000 claims abstract description 47
- 239000002114 nanocomposite Substances 0.000 claims abstract description 47
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 230000015556 catabolic process Effects 0.000 claims abstract description 21
- 238000006731 degradation reaction Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000011159 matrix material Substances 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims description 49
- 239000005030 aluminium foil Substances 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 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 17
- 229940012189 methyl orange Drugs 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229960000789 guanidine hydrochloride Drugs 0.000 claims description 3
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 239000011888 foil Substances 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000011941 photocatalyst Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- 238000004140 cleaning Methods 0.000 description 14
- 239000007921 spray Substances 0.000 description 13
- 230000001699 photocatalysis Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- -1 silver halide Chemical class 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229940073609 bismuth oxychloride Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of PVDF-Ag/AgBr/g-C3N4The preparation method of-BiOCl (001) composite membrane, belongs to photocatalyst technology field.The composite membrane active component is Ag/AgBr/g-C3N4With BiOCl (001), structure is Ag/AgBr/g-C3N4It is distributed in PVDF matrix with BiOCl (001).The present invention first uses BiOCl (001) to adulterate PVDF, is then introducing Ag/AgBr/g-C3N4Nanocomposite is combined using the SPR effect and crystal face engineering technology of noble metal, the separation and transmission of light induced electron is optimized, to improve catalytic activity.Reaction for the MO that degrades, when being photochemical catalyst with the composite membrane, 30W LED light is as light source, and when irradiation time is 120min, the degradation rate of MO reaches 92%.
Description
Technical field
The invention belongs to photochemical catalyst fields, and in particular to a kind of bismuth oxychloride (BiOCl (001)) in exposure (001) face
With nanocomposite Ag/AgBr/g-C3N4Doping gathers inclined tetrafluoroethene (PVDF) composite membrane, and (this composite membrane is abbreviated as PVDF-
Ag/AgBr/g‐C3N4- BiOCl (001)) technology of preparing, in particular to a kind of pattern and form controllable PVDF-Ag/AgBr/
g‐C3N4The technology of preparing of-BiOCl (001) composite membrane.The present invention closes prepared PVDF-Ag/AgBr/g-C3N4‐BiOCl
(001) composite membrane is photochemical catalyst, achieves good catalytic effect for Photodegradation of Methyl Orange (MO).
Background technique
Environmental problem and energy problem are the two big challenges that 21 century human kind sustainable development faces.Utilize clean solar energy
The Photocatalitic Technique of Semiconductor of resource, which becomes, copes with one of the important means of this two big challenge (S.Bai, et al.Steering
charge kinetics in photocatalysis:intersection of materials syntheses,
characterization techniques and theoretical simulations,Chem.Soc.Rev.,44
(2015) 2893‐2939.).But the research of catalysis material at present still suffers from and limits the following heavy of its practical application
Want problem: first is that optical response range is narrow.Conventional semiconductors with high activity, such as TiO2, energy band is wider, can only absorb and account for
The ultraviolet light of solar energy 4% or so can not cause solar energy utilization ratio lower using the most visible light of solar energy is accounted for.Two
It is that the catalysis oxidation efficiency is low.The light induced electron generated under illumination and hole is inside semiconductor or surface is compound rapidly, Wu Fayou
The participation photocatalytic process of effect, causes the catalysis oxidation efficiency lower.Third is that there is still a need for further researchs for catalytic mechanism.Promote light
The most popular method of raw electrons and holes separation first is that building hetero-junctions, since photocatalytic process is sufficiently complex, in its catalysis
In terms of mechanism study, although having done a lot of research work, at present still also not to the catalytic mechanism of complex heterogeneous knot
It is fully aware of.Fourth is that catalyst cured difficulty, leads to catalyst loss, secondary pollution problems (H.Wang, et al. is caused
Semiconductor heterojunction photocatalysts:design,construction,and
photocatalytic performances,Chem.Soc.Rev.,2014,43,5234‐5244；N.Zhang,et al.
Waltzing with the Versatile Platform of Graphene to Synthesize Composite
Photocatalysts,Chem.Rev.2015,115,10307‐10377.)。
Class graphite phase carbon nitride (g-C3N4) since special optical characteristics is often used as photochemical catalyst, it is controlled in environmental pollution
Reason, clean energy resource regeneration etc. (Z.Zhao, et al.Graphitic the carbon nitride that has broad application prospects
based nanocomposites:a review,Nanoscale,2015,7,15‐37；Y.He,et al.New
Application of Z‐Scheme Ag3PO4/g‐C3N4Composite in Converting CO2to Fuel,
Environ.Sci.Technol.,2015,49,649‐656).But g-C3N4Structure be stratiform two-dimensional structure, layer and layer it
Between atom hydridization degree it is low, greater band gap, cause it only ultraviolet region respond.Research shows that in g-C3N4Middle doping is other
Element or compound can change g-C3N4Band gap, enhance interlayer atom interaction, widen g-C3N4Response section,
Improve g-C3N4Photocatalysis efficiency.Meanwhile passing through the material of other structures such as BiOBr etc. and g-C3N4Compound (L.Ye, et
al.Facets coupling of BiOBr‐g‐C3N4composite photocatalyst for enhanced
visible‐light‐driven photocatalytic activity.Appl.Catal.B‐Environ,2013,142,1‐
7), hence it is evident that improve the photocatalysis performance of composite material under visible light, reason essentially consists in compound interface and promotes photoproduction
Carrier efficiently separates.Researches show that silver halide (AgX, X=Cl, Br) and g-C3N4Between there are synergistic effect, matched energy
Grade promotes the migration and separation of photo-generated carrier, enhances compound to the absorbability of visible light, to improve the light of Ag/AgX
Catalytic activity.Therefore, by the supported processing of plasma material, can enhance plasma photocatalysis composite material etc.
Gas ions resonance effects improves the absorbability to visible light, promotes efficiently separating for photo-generated carrier, to improve catalyst
Activity and stability.
Photocatalysis membrana can curing nano photochemical catalyst, reduce and catalyst loss and cause secondary pollution etc., be widely applied
In water treatment field (Q.Cao, et al., Porous Au-Ag Alloy Particles Inlaid AgCl Membranes
As Versatile Plasmonic Catalytic Interfaces with Simultaneous,in Situ SERS
Monitoring,ACS Appl.Mater.Interfaces,2015,33,18491‐18500；F.Persico,et al.,
Photocatalytic activity of TiO2‐embedded fluorinated transparent coating for
oxidation of hydrosoluble pollutants in turbid suspensions,Appl.Catal.B‐
Environ. 2015,170,83‐89).Membrane material mainly has ceramic membrane and macromolecule organic film, and light-catalyzed reaction is to inorganic pottery
The chemical damage of porcelain film is smaller, can better meet test stability requirement.But ceramic membrane is expensive, using by
It restricts.Therefore, reasonable selection is widely used and the polymerization macromolecule organic film of relative low price is as photo catalysis reactor
Coupled separation membrane will be the importance that its industrialization is used.The common high molecular material of organic film mainly has polytetrafluoroethylene (PTFE)
(PTFE), Kynoar (PVDF), polyacrylonitrile (PAN) etc., wherein the stability of PVDF is best.Nano-photocatalyst
There are mainly two types of the methods that grain is coupled with film: first is that catalyst granules is blended in the matrix of film, but this method makes
The activity of catalyst is greatly lowered.Second is that catalyst granules is inlayed (J.P.M é ricq, et on the surface of the catalyst
al.,High performance PVDF‐TiO2membranes for water treatment,Chem.Eng.Sci,
2015,123,283-291.), still, this method is easy that catalyst granules is made to reunite, and also its catalytic activity can in this way dropped
It is low.In order to reduce the reunion of nano-catalyst particles, Ag/AgBr nanosphere is first grown in g-C by this patent3N4In nanometer sheet, shape
At Ag/AgBr/g-C3N4Nanocomposite is doped in PVDF matrix, in order to further increase its catalytic performance, this patent
BiOCl (001) is introduced into PVDF matrix first, is then re-introduced into Ag/AgBr/g-C3N4Nanocomposite forms PVDF-
Ag/AgBr/g‐C3N4- BiOCl (001) composite membrane.BiOCl (001) nanocrystal interior there are magnetic field and different crystal face it
Between there are potential difference, play the role of separating photo-generate electron-hole, i.e. electronics is flowed to low potential, and vacancy is flowed to high potential,
To be conducive to improve its photocatalytic activity (S.Bai, et al., Steering charge kinetics in
photocatalysis:intersection of materials syntheses,characterization
techniques and theoretical simulations, Chem.Soc.Rev.,2015,44,2893‐2939.).This
Invention prepares PVDF-Ag/AgBr/g-C using multicomponent, manifold effect3N4- BiOCl (001) composite membrane, and for degrading MO not
It appears in the newspapers.
Summary of the invention
It is an object of the present invention to provide a kind of pattern and form controllable PVDF-Ag/AgBr/g-C3N4- BiOCl (001) is multiple
The preparation method of film is closed, to use PVDF-Ag/AgBr/g-C prepared by the present invention3N4- BiOCl (001) composite membrane is urged as light
Agent degradation MO obtains good effect.
In order to achieve the above technical purposes, the present invention is achieved by the following technical programs.
The present invention provides a kind of PVDF-Ag/AgBr/g-C3N4- BiOCl (001) composite membrane, active component is Ag/
AgBr/g‐C3N4With BiOCl (001), structure is Ag/AgBr/g-C3N4It is distributed in PVDF matrix with BiOCl (001),
Its specific preparation process is as follows:
Weigh the guanidine hydrochloride and NH that mass ratio is 1:14Cl ground and mixed in mortar is uniform, is placed in Muffle furnace 600 DEG C
Calcining, obtained product is exactly g-C3N4Nanometer sheet.
It measures 12mL ethylene glycol and is put into round-bottomed flask, constant temperature stirs 30min at 105 DEG C, and 95mg PVP and 120mg is added
Cetyl trimethylammonium bromide (CTAB) continues stirring until the two is completely dissolved, and then addition 25mg makes in aforementioned manners
Standby g-C3N4, continue to stir 2h, so that g-C3N4It is evenly distributed in above-mentioned solution, suspension at this time is referred to as A.In addition
100mg AgNO is weighed at normal temperature3, dissolve it in 1.5mL ethylene glycol, referred to as solution B.While stirring, with modeling
Drop pipe instills solution B in suspending liquid A, stirs 30min, and temperature is risen to 155 DEG C, keeps 15min, reaction terminates.It will be anti-
It answers object to be cooled to room temperature, is centrifugated, washing obtains Ag/AgBr/g-C after dry3N4Nanocomposite.
Sodium chloride 146mg, enuatrol (NaOA) 100mg are weighed, 30mL deionized water is added, 75 DEG C of stirring 30min make oil
Sour sodium and NaCl sufficiently dissolve, and the 0.5mol/L Bi (NO of 2mL is slowly added into round-bottomed flask3)3, and in the lower reaction of 95 DEG C of degree
3 hours, reactant is cooled to room temperature, is centrifugated, washing obtains solid product after dry, which is BiOCl
(001)。
The ground BiOCl of 5~30mg (001) powder is weighed in centrifuge tube, 1~3mL dehydrated alcohol is added；Weigh 5
~30mg Ag/AgBr/g-C3N41~3mL dehydrated alcohol is added in centrifuge tube in powder；Weigh 5~30mg PVDF be placed in from
In heart pipe, 1~3mL 1-Methyl-2-Pyrrolidone is added.3 centrifuge tubes are put into supersonic cleaning machine and are vibrated 5 minutes.Two
Suspension is formed in pipe, forms transparence liquid in another pipe.The aluminium foil of clip 6cm × 6cm makes its surfacing, four
It turns up on a side.Solution made of PVDF is poured into sprayer first, is then uniformly sprayed in aluminium foil bottom surface；Equally
Successively by BiOCl (001) suspension, Ag/AgBr/g-C3N4Uniform suspension is sprayed on aluminium foil bottom surface.Then it puts
Enter drying in drying box, PVDF-Ag/AgBr/g-C can be obtained after 30min3N4- BiOCl (001) composite membrane.
By adjusting BiOCl (001), ethyl alcohol, Ag/AgBr/g-C3N4, PVDF and the dosage of 1-Methyl-2-Pyrrolidone etc.
Preparation condition can control PVDF-Ag/AgBr/g-C3N4The pattern and composition of-BiOCl (001) composite membrane.When BiOCl (001),
Ethyl alcohol, Ag/AgBr/g-C3N4, PVDF and 1-Methyl-2-Pyrrolidone dosage be respectively 10mg, 2mL, 20mg, 15mg and
When 1mL, Ag/AgBr/g-C3N4It is uniformly dispersed in PVDF with BiOCl (001).
PVDF-Ag/AgBr/g-C prepared by the present invention3N4- BiOCl (001) composite membrane can be used as photochemical catalyst for degrading
When MO, good catalytic effect is shown.PVDF-Ag/AgBr/g-C prepared by the present invention3N4- BiOCl (001) composite membrane
Reaction condition when for light degradation MO are as follows: concentration is 10mg mL-1MO aqueous solution 10mL, 30W LED light be light source, when irradiation
Between when being 120min, degradation rate reaches 92%.In addition, the catalyst is also with good stability, the above-mentioned MO of catalytic degradation
Aqueous solution, continuous circulation 6 times, degradation rate still is able to reach 87%.
Compared with prior art, catalytic degradation MO is used for using catalyst of the present invention, had the advantage that
(1) Ag/AgBr is grown in g-C3N4In nanometer sheet, then in doping PVDF, Ag/AgBr glue can be effectively prevented
Reunion of the body ball in PVDF matrix.
(2) high catalytic efficiency；
This composite membrane is by Ag/AgBr/g-C3N4Nanocomposite and BiOCl (001) composition, precious metals ag generate surface
Plasma resonance effect (SPR) increases the absorption to visible light, typically uses TiO relatively2The PVDF composite membrane of doping comes
It says, light absorbing wave-length coverage increases, and improves the utilization rate of sunlight.
(3) activity of catalyst is high；
The preparation of the composite membrane uses the strategy of multicomponent, manifold effect, and catalytic activity dramatically increases.This patent is first used
BiOCl (001) adulterates PVDF, is then introducing Ag/AgBr/g-C3N4Nanocomposite, using noble metal SPR effect and
Crystal face engineering technology combines, and the separation and transmission of light induced electron is optimized, to improve catalytic activity.For degradation MO's
Reaction, when being photochemical catalyst with the composite membrane, 30W LED lamp is as light source, when irradiation time is 120min, the degradation of MO
Rate reaches 92%.
(4) catalytic stability is good；
Catalytic degradation MO aqueous solution, continuous circulation 6 times, degradation rate still is able to reach 87%.
Detailed description of the invention
Fig. 1 is PVDF-Ag/AgBr/g-C prepared by the embodiment of the present invention 13N4- BiOCl (001) composite membrane scanning electron microscope
Photo (amplification factor of a, b are different)；
Ag/AgBr colloidal spheres are first grown in g-C it can be seen from Fig. 1 (a)3N4In nanometer sheet, can effectively it prevent
It is reunited.Since what is first introduced is BiOCl (001) nanometer sheet, below the composite membrane partially mainly BiOCl (001)
Nanometer sheet, upper part are mainly Ag/AgBr/g-C3N4；By shown in Fig. 1 (b), big gap is conducive to incident light in composite membrane
Entrance and mass transfer, to improve its catalytic effect.
Specific embodiment
Feature of the invention is described further below by example, but the present invention is not limited to following embodiments.
One, PVDF-Ag/AgBr/g-C3N4The preparation of-BiOCl (001) composite membrane
Embodiment 1
1#PVDF‐Ag/AgBr/g‐C3N4Specific preparation process is as follows for-BiOCl (001) composite membrane:
(1)g‐C3N4Preparation
Weigh 2.5g guanidine hydrochloride and 2.5g NH4Cl ground and mixed in mortar is uniform, is placed on 600 DEG C of calcinings in Muffle furnace
2h 45min, obtained product are exactly g-C3N4Nanometer sheet, stereoscan photograph are as shown in Figure 1.
(2)Ag/AgBr/g‐C3N4The preparation of nanocomposite
It measures 12mL ethylene glycol and is put into round-bottomed flask, constant temperature stirs 30min at 105 DEG C, and 95mg PVP and 120mg is added
CTAB continues to stir the g-C up to the two is completely dissolved, and then addition 5mg is prepared in aforementioned manners3N4, continue to stir 2h, with
Make g-C3N4It is evenly distributed in above-mentioned solution, suspension at this time is referred to as A.In addition 100mg AgNO is weighed at normal temperature3,
It dissolves it in 1.5mL ethylene glycol, referred to as solution B.While stirring, solution B is instilled suspending liquid A with plastic dropper
In, 30min is stirred, temperature is appreciated 155 DEG C, stirring 15min reaction terminates.Reactant is cooled to room temperature, is centrifugated, washes
It washs, obtains Ag/AgBr/g-C after dry3N4Nanocomposite.
(3) preparation of BiOCl (001)
Sodium chloride 146mg, enuatrol (NaOA) 100mg are weighed, 30mL deionized water is added, 75 DEG C of stirring 30min make oil
Sour sodium and NaCl sufficiently dissolve, and the 0.5mol/L Bi (NO of 2mL is slowly added into round-bottomed flask3)3, and in the lower reaction of 95 DEG C of degree
3 hours, reactant is cooled to room temperature, is centrifugated, washing obtains solid product after dry, which is BiOCl
(001)。
(4)PVDF‐Ag/AgBr/g‐C3N4The preparation of-BiOCl (001) composite membrane
The ground BiOCl of 10mg (001) powder is weighed in centrifuge tube, 1ml dehydrated alcohol is added；Weigh 20mg Ag/
AgBr/g‐C3N42mL dehydrated alcohol is added in centrifuge tube in powder；It weighs 15mg PVDF to be placed in centrifuge tube, 1mL is added
1-Methyl-2-Pyrrolidone.3 centrifuge tubes are put into supersonic cleaning machine and are vibrated 5 minutes.Suspension is formed in two pipes, separately
Transparence liquid is formed in one pipe.The aluminium foil of clip 6cm × 6cm makes its surfacing.First by solution made of PVDF
It pours into sprayer, then uniformly sprays in aluminium foil surface；Similarly successively by BiOCl (001) suspension, Ag/AgBr/g-
C3N4Uniform suspension is sprayed on aluminium foil surface.It is then placed in drying in drying box, PVDF-Ag/ can be obtained after 30min
AgBr/g‐ C3N4- BiOCl (001) composite membrane.
Embodiment 2
2#Ag/AgBr/g‐C3N4Specific preparation process is as follows for nanocomposite:
(1)g‐C3N4Preparation
With g-C in embodiment 13N4Preparation method.
(2)Ag/AgBr/g‐C3N4The preparation of nanocomposite
With Ag/AgBr/g-C in embodiment 13N4The preparation method of nanocomposite.
(3) preparation of BiOCl (001)
With the preparation method of BiOCl (001) in embodiment 1.
(4)PVDF‐Ag/AgBr/g‐C3N4The preparation of-BiOCl (001) composite membrane
The ground BiOCl of 5mg (001) powder is weighed in centrifuge tube, 1ml dehydrated alcohol is added；Weigh 20mg Ag/
AgBr/g‐C3N42mL dehydrated alcohol is added in centrifuge tube in powder；It weighs 15mg PVDF to be placed in centrifuge tube, 1mL is added
1-Methyl-2-Pyrrolidone.3 centrifuge tubes are put into supersonic cleaning machine and are vibrated 5 minutes.Suspension is formed in two pipes, separately
Transparence liquid is formed in one pipe.The aluminium foil of clip 6cm × 6cm makes its surfacing.First by solution made of PVDF
It pours into sprayer, then uniformly sprays in aluminium foil surface；Similarly successively by BiOCl (001) suspension, Ag/AgBr/g-
C3N4Uniform suspension is sprayed on aluminium foil surface.It is then placed in drying in drying box, PVDF-Ag/ can be obtained after 30min
AgBr/g‐ C3N4- BiOCl (001) composite membrane.
Embodiment 3
3#Ag/AgBr/g‐C3N4Specific preparation process is as follows for nanocomposite:
(1)g‐C3N4Preparation
With g-C in embodiment 13N4Preparation method.
(2)Ag/AgBr/g‐C3N4The preparation of nanocomposite
With Ag/AgBr/g-C in embodiment 13N4The preparation method of nanocomposite.
(3) preparation of BiOCl (001)
With the preparation method of BiOCl (001) in embodiment 1.
(4)PVDF‐Ag/AgBr/g‐C3N4The preparation of-BiOCl (001) composite membrane
The ground BiOCl of 30mg (001) powder is weighed in centrifuge tube, 1ml dehydrated alcohol is added；Weigh 20mg Ag/
AgBr/g‐C3N42mL dehydrated alcohol is added in centrifuge tube in powder；It weighs 15mg PVDF to be placed in centrifuge tube, 1mL is added
1-Methyl-2-Pyrrolidone.3 centrifuge tubes are put into supersonic cleaning machine and are vibrated 5 minutes.Suspension is formed in two pipes, separately
Transparence liquid is formed in one pipe.The aluminium foil of clip 6cm × 6cm makes its surfacing.First by solution made of PVDF
It pours into sprayer, then uniformly sprays in aluminium foil surface；Similarly successively by BiOCl (001) suspension, Ag/AgBr/g-
C3N4Uniform suspension is sprayed on aluminium foil surface.It is then placed in drying in drying box, PVDF-Ag/ can be obtained after 30min
AgBr/g‐ C3N4- BiOCl (001) composite membrane.
Embodiment 4
4#Ag/AgBr/g‐C3N4Specific preparation process is as follows for nanocomposite:
(1)g‐C3N4Preparation
With g-C in embodiment 13N4Preparation method.
(2)Ag/AgBr/g‐C3N4The preparation of nanocomposite
With Ag/AgBr/g-C in embodiment 13N4The preparation method of nanocomposite.
(3) preparation of BiOCl (001)
With the preparation method of BiOCl (001) in embodiment 1.
(4)PVDF‐Ag/AgBr/g‐C3N4The preparation of-BiOCl (001) composite membrane
The ground BiOCl of 10mg (001) powder is weighed in centrifuge tube, 2ml dehydrated alcohol is added；Weigh 20mg Ag/
AgBr/g‐C3N42mL dehydrated alcohol is added in centrifuge tube in powder；It weighs 15mg PVDF to be placed in centrifuge tube, 1mL is added
1-Methyl-2-Pyrrolidone.3 centrifuge tubes are put into supersonic cleaning machine and are vibrated 5 minutes.Suspension is formed in two pipes, separately
Transparence liquid is formed in one pipe.The aluminium foil of clip 6cm × 6cm makes its surfacing.First by solution made of PVDF
It pours into sprayer, then uniformly sprays in aluminium foil surface；Similarly successively by BiOCl (001) suspension, Ag/AgBr/g-
C3N4Uniform suspension is sprayed on aluminium foil surface.It is then placed in drying in drying box, PVDF-Ag/ can be obtained after 30min
AgBr/g‐ C3N4- BiOCl (001) composite membrane.
Embodiment 5
5#Ag/AgBr/g‐C3N4Specific preparation process is as follows for nanocomposite:
(1)g‐C3N4Preparation
With g-C in embodiment 13N4Preparation method.
(2)Ag/AgBr/g‐C3N4The preparation of nanocomposite
With Ag/AgBr/g-C in embodiment 13N4The preparation method of nanocomposite.
(3) preparation of BiOCl (001)
With the preparation method of BiOCl (001) in embodiment 1.
(4)PVDF‐Ag/AgBr/g‐C3N4The preparation of-BiOCl (001) composite membrane
The ground BiOCl of 10mg (001) powder is weighed in centrifuge tube, 3ml dehydrated alcohol is added；Weigh 20mg Ag/
AgBr/g‐C3N42mL dehydrated alcohol is added in centrifuge tube in powder；It weighs 15mg PVDF to be placed in centrifuge tube, 1mL is added
1-Methyl-2-Pyrrolidone.3 centrifuge tubes are put into supersonic cleaning machine and are vibrated 5 minutes.Suspension is formed in two pipes, separately
Transparence liquid is formed in one pipe.The aluminium foil of clip 6cm × 6cm makes its surfacing.First by solution made of PVDF
It pours into sprayer, then uniformly sprays in aluminium foil surface；Similarly successively by BiOCl (001) suspension, Ag/AgBr/g-
C3N4Uniform suspension is sprayed on aluminium foil surface.It is then placed in drying in drying box, PVDF-Ag/ can be obtained after 30min
AgBr/g‐ C3N4- BiOCl (001) composite membrane.
Embodiment 6
6#Ag/AgBr/g‐C3N4Specific preparation process is as follows for nanocomposite:
(1)g‐C3N4Preparation
With g-C in embodiment 13N4Preparation method.
(2)Ag/AgBr/g‐C3N4The preparation of nanocomposite
With Ag/AgBr/g-C in embodiment 13N4The preparation method of nanocomposite.
(3) preparation of BiOCl (001)
With the preparation method of BiOCl (001) in embodiment 1.
(4)PVDF‐Ag/AgBr/g‐C3N4The preparation of-BiOCl (001) composite membrane
The ground BiOCl of 10mg (001) powder is weighed in centrifuge tube, 1ml dehydrated alcohol is added；Weigh 5mg Ag/
AgBr/g‐C3N42mL dehydrated alcohol is added in centrifuge tube in powder；It weighs 15mg PVDF to be placed in centrifuge tube, 1mL is added
1-Methyl-2-Pyrrolidone.3 centrifuge tubes are put into supersonic cleaning machine and are vibrated 5 minutes.Suspension is formed in two pipes, separately
Transparence liquid is formed in one pipe.The aluminium foil of clip 6cm × 6cm makes its surfacing.First by solution made of PVDF
It pours into sprayer, then uniformly sprays in aluminium foil surface；Similarly successively by BiOCl (001) suspension, Ag/AgBr/g-
C3N4Uniform suspension is sprayed on aluminium foil surface.It is then placed in drying in drying box, PVDF-Ag/ can be obtained after 30min
AgBr/g‐ C3N4- BiOCl (001) composite membrane.
Embodiment 7
7#Ag/AgBr/g‐C3N4Specific preparation process is as follows for nanocomposite:
(1)g‐C3N4Preparation
With g-C in embodiment 13N4Preparation method.
(2)Ag/AgBr/g‐C3N4The preparation of nanocomposite
With Ag/AgBr/g-C in embodiment 13N4The preparation method of nanocomposite.
(3) preparation of BiOCl (001)
With the preparation method of BiOCl (001) in embodiment 1.
(4)PVDF‐Ag/AgBr/g‐C3N4The preparation of-BiOCl (001) composite membrane
The ground BiOCl of 10mg (001) powder is weighed in centrifuge tube, 1ml dehydrated alcohol is added；Weigh 30mg Ag/
AgBr/g‐C3N42mL dehydrated alcohol is added in centrifuge tube in powder；It weighs 15mg PVDF to be placed in centrifuge tube, 1mL is added
1-Methyl-2-Pyrrolidone.3 centrifuge tubes are put into supersonic cleaning machine and are vibrated 5 minutes.Suspension is formed in two pipes, separately
Transparence liquid is formed in one pipe.The aluminium foil of clip 6cm × 6cm makes its surfacing.First by solution made of PVDF
It pours into sprayer, then uniformly sprays in aluminium foil surface；Similarly successively by BiOCl (001) suspension, Ag/AgBr/g-
C3N4Uniform suspension is sprayed on aluminium foil surface.It is then placed in drying in drying box, PVDF-Ag/ can be obtained after 30min
AgBr/g‐ C3N4- BiOCl (001) composite membrane.
Embodiment 8
8#Ag/AgBr/g‐C3N4Specific preparation process is as follows for nanocomposite:
(1)g‐C3N4Preparation
With g-C in embodiment 13N4Preparation method.
(2)Ag/AgBr/g‐C3N4The preparation of nanocomposite
With Ag/AgBr/g-C in embodiment 13N4The preparation method of nanocomposite.
(3) preparation of BiOCl (001)
With the preparation method of BiOCl (001) in embodiment 1.
(4)PVDF‐Ag/AgBr/g‐C3N4The preparation of-BiOCl (001) composite membrane
The ground BiOCl of 10mg (001) powder is weighed in centrifuge tube, 1ml dehydrated alcohol is added；Weigh 20mg Ag/
AgBr/g‐C3N41mL dehydrated alcohol is added in centrifuge tube in powder；It weighs 15mg PVDF to be placed in centrifuge tube, 1mL is added
1-Methyl-2-Pyrrolidone.3 centrifuge tubes are put into supersonic cleaning machine and are vibrated 5 minutes.Suspension is formed in two pipes, separately
Transparence liquid is formed in one pipe.The aluminium foil of clip 6cm × 6cm makes its surfacing.First by solution made of PVDF
It pours into sprayer, then uniformly sprays in aluminium foil surface；Similarly successively by BiOCl (001) suspension, Ag/AgBr/g-
C3N4Uniform suspension is sprayed on aluminium foil surface.It is then placed in drying in drying box, PVDF-Ag/ can be obtained after 30min
AgBr/g‐ C3N4- BiOCl (001) composite membrane.
Embodiment 9
9#Ag/AgBr/g‐C3N4Specific preparation process is as follows for nanocomposite:
(1)g‐C3N4Preparation
With g-C in embodiment 13N4Preparation method.
(2)Ag/AgBr/g‐C3N4The preparation of nanocomposite
With Ag/AgBr/g-C in embodiment 13N4The preparation method of nanocomposite.
(3) preparation of BiOCl (001)
With the preparation method of BiOCl (001) in embodiment 1.
(4)PVDF‐Ag/AgBr/g‐C3N4The preparation of-BiOCl (001) composite membrane
The ground BiOCl of 10mg (001) powder is weighed in centrifuge tube, 1ml dehydrated alcohol is added；Weigh 20mg Ag/
AgBr/g‐C3N43mL dehydrated alcohol is added in centrifuge tube in powder；It weighs 15mg PVDF to be placed in centrifuge tube, 1mL is added
1-Methyl-2-Pyrrolidone.3 centrifuge tubes are put into supersonic cleaning machine and are vibrated 5 minutes.Suspension is formed in two pipes, separately
Transparence liquid is formed in one pipe.The aluminium foil of clip 6cm × 6cm makes its surfacing.First by solution made of PVDF
It pours into sprayer, then uniformly sprays in aluminium foil surface；Similarly successively by BiOCl (001) suspension, Ag/AgBr/g-
C3N4Uniform suspension is sprayed on aluminium foil surface.It is then placed in drying in drying box, PVDF-Ag/ can be obtained after 30min
AgBr/g‐ C3N4- BiOCl (001) composite membrane.
Embodiment 10
10#Ag/AgBr/g‐C3N4Specific preparation process is as follows for nanocomposite:
(1)g‐C3N4Preparation
With g-C in embodiment 13N4Preparation method.
(2)Ag/AgBr/g‐C3N4The preparation of nanocomposite
With Ag/AgBr/g-C in embodiment 13N4The preparation method of nanocomposite.
(3) preparation of BiOCl (001)
With the preparation method of BiOCl (001) in embodiment 1.
(4)PVDF‐Ag/AgBr/g‐C3N4The preparation of-BiOCl (001) composite membrane
The ground BiOCl of 10mg (001) powder is weighed in centrifuge tube, 1ml dehydrated alcohol is added；Weigh 20mg Ag/
AgBr/g‐C3N42mL dehydrated alcohol is added in centrifuge tube in powder；It weighs 5mg PVDF to be placed in centrifuge tube, 1mL 1- is added
N-methyl-2-2-pyrrolidone N.3 centrifuge tubes are put into supersonic cleaning machine and are vibrated 5 minutes.Suspension is formed in two pipes, it is another
Transparence liquid is formed in a pipe.The aluminium foil of clip 6cm × 6cm makes its surfacing.Solution made of PVDF is fallen first
Enter in sprayer, then uniformly sprays in aluminium foil surface；Similarly successively by BiOCl (001) suspension, Ag/AgBr/g-
C3N4Uniform suspension is sprayed on aluminium foil surface.It is then placed in drying in drying box, PVDF-Ag/ can be obtained after 30min
AgBr/g‐ C3N4- BiOCl (001) composite membrane.
Embodiment 11
11#Ag/AgBr/g‐C3N4Specific preparation process is as follows for nanocomposite:
(1)g‐C3N4Preparation
With g-C in embodiment 13N4Preparation method.
(2)Ag/AgBr/g‐C3N4The preparation of nanocomposite
With Ag/AgBr/g-C in embodiment 13N4The preparation method of nanocomposite.
(3) preparation of BiOCl (001)
With the preparation method of BiOCl (001) in embodiment 1.
(4)PVDF‐Ag/AgBr/g‐C3N4The preparation of-BiOCl (001) composite membrane
The ground BiOCl of 10mg (001) powder is weighed in centrifuge tube, 1ml dehydrated alcohol is added；Weigh 20mg Ag/
AgBr/g‐C3N42mL dehydrated alcohol is added in centrifuge tube in powder；It weighs 30mg PVDF to be placed in centrifuge tube, 1mL is added
1-Methyl-2-Pyrrolidone.3 centrifuge tubes are put into supersonic cleaning machine and are vibrated 5 minutes.Suspension is formed in two pipes, separately
Transparence liquid is formed in one pipe.The aluminium foil of clip 6cm × 6cm makes its surfacing.First by solution made of PVDF
It pours into sprayer, then uniformly sprays in aluminium foil surface；Similarly successively by BiOCl (001) suspension, Ag/AgBr/g-
C3N4Uniform suspension is sprayed on aluminium foil surface.It is then placed in drying in drying box, PVDF-Ag/ can be obtained after 30min
AgBr/g‐ C3N4- BiOCl (001) composite membrane.
Embodiment 12
12#Ag/AgBr/g‐C3N4Specific preparation process is as follows for nanocomposite:
(1)g‐C3N4Preparation
With g-C in embodiment 13N4Preparation method.
(2)Ag/AgBr/g‐C3N4The preparation of nanocomposite
With Ag/AgBr/g-C in embodiment 13N4The preparation method of nanocomposite.
(3) preparation of BiOCl (001)
With the preparation method of BiOCl (001) in embodiment 1.
(4)PVDF‐Ag/AgBr/g‐C3N4The preparation of-BiOCl (001) composite membrane
The ground BiOCl of 10mg (001) powder is weighed in centrifuge tube, 1ml dehydrated alcohol is added；Weigh 20mg Ag/
AgBr/g‐C3N42mL dehydrated alcohol is added in centrifuge tube in powder；It weighs 15mg PVDF to be placed in centrifuge tube, 2mL is added
1-Methyl-2-Pyrrolidone.3 centrifuge tubes are put into supersonic cleaning machine and are vibrated 5 minutes.Suspension is formed in two pipes, separately
Transparence liquid is formed in one pipe.The aluminium foil of clip 6cm × 6cm makes its surfacing.First by solution made of PVDF
It pours into sprayer, then uniformly sprays in aluminium foil surface；Similarly successively by BiOCl (001) suspension, Ag/AgBr/g-
C3N4Uniform suspension is sprayed on aluminium foil surface.It is then placed in drying in drying box, PVDF-Ag/ can be obtained after 30min
AgBr/g‐ C3N4- BiOCl (001) composite membrane.
Embodiment 13
13#Ag/AgBr/g‐C3N4Specific preparation process is as follows for nanocomposite:
(1)g‐C3N4Preparation
With g-C in embodiment 13N4Preparation method.
(2)Ag/AgBr/g‐C3N4The preparation of nanocomposite
With Ag/AgBr/g-C in embodiment 13N4The preparation method of nanocomposite.
(3) preparation of BiOCl (001)
With the preparation method of BiOCl (001) in embodiment 1.
(4)PVDF‐Ag/AgBr/g‐C3N4The preparation of-BiOCl (001) composite membrane
The ground BiOCl of 10mg (001) powder is weighed in centrifuge tube, 1ml dehydrated alcohol is added；Weigh 20mg Ag/
AgBr/g‐C3N42mL dehydrated alcohol is added in centrifuge tube in powder；It weighs 15mg PVDF to be placed in centrifuge tube, 3mL is added
1-Methyl-2-Pyrrolidone.3 centrifuge tubes are put into supersonic cleaning machine and are vibrated 5 minutes.Suspension is formed in two pipes, separately
Transparence liquid is formed in one pipe.The aluminium foil of clip 6cm × 6cm makes its surfacing.First by solution made of PVDF
It pours into sprayer, then uniformly sprays in aluminium foil surface；Similarly successively by BiOCl (001) suspension, Ag/AgBr/g-
C3N4Uniform suspension is sprayed on aluminium foil surface.It is then placed in drying in drying box, PVDF-Ag/ can be obtained after 30min
AgBr/g‐ C3N4- BiOCl (001) composite membrane.
Two, PVDF-Ag/AgBr/g-C3N4Activity rating of-BiOCl (001) composite membrane as catalyst
Table 1:PVDF-Ag/AgBr/g-C3N4- BiOCl (001) composite membrane photocatalytic degradation MO experimental result
(a)Reaction condition: degradation concentration is 10mg L-1MO solution 10mL
Measure 10mL 10mg L-1MO aqueous solution is put on the aluminium foil that four sides are all turned up prepared by above-described embodiment 1, is used
30W LED light irradiates 2h, every the 20min concentration of MO in 722S spectrophotometer measurement aqueous solution.Table 1 is that institute of the invention is real
Apply PVDF-Ag/AgBr/g-C prepared by example 13N4The degradation rate of difference light application time when-BiOCl (001), degradation MO.From table
In 1 as can be seen that under the irradiation of 30W LED light, PVDF-Ag/ AgBr/g-C3N4- BiOCl (001) shows degradation MO
Good catalytic activity.When irradiating 40min, the degradation rate of MO is 69%, and when light application time is 60min, degradation rate reaches
80%, when light application time is 120 min, degradation rate reaches 92%.
Table 2:PVDF-Ag/AgBr/g-C3N4The stability experiment result of-BiOCl (001) photochemical catalyst
Table 2 is catalyst PVDF-Ag/AgBr/g-C prepared by embodiment 13N4The stability test of-BiOCl (001).
Degradation 10mL concentration is 10mg L-1MO aqueous solution, light application time 2h is coated with PVDF-Ag/AgBr/g- after completion of the reaction
C3N4The aluminium foil of-BiOCl (001) recycles, and adding 10mL concentration is 10mg L-1MO aqueous solution carries out exposure experiments to light, the aluminium foil
It is so recycled 6 times, from Table 2, it can be seen that the degradation rate of MO still can reach 87%, this shows: PVDF-Ag/AgBr/
g‐C3N4- BiOCl (001) composite membrane has good stability.
Claims (3)
1. a kind of PVDF-Ag/AgBr/g-C3N4The preparation method of-BiOCl (001) composite membrane, which is characterized in that the composite membrane is living
Property component is Ag/AgBr/g-C3N4With BiOCl (001), structure is Ag/AgBr/g-C3N4It is distributed in BiOCl (001)
In PVDF matrix, specific preparation process is as follows:
(1)g‐C3N4Preparation
Weigh the guanidine hydrochloride and NH that mass ratio is 1:14Cl ground and mixed in mortar is uniform, is placed on 600 DEG C of calcinings in Muffle furnace,
Obtained product is exactly g-C3N4Nanometer sheet；
(2)Ag/AgBr/g‐C3N4The preparation of nanocomposite
It measures 12mL ethylene glycol and is put into round-bottomed flask, constant temperature stirs 30min at 105 DEG C, and 95mg PVP and 120mg is added
CTAB, continue stirring until both be completely dissolved, then be added 25mg step (1) preparation g-C3N4, continue to stir 2h, so that
g‐C3N4It is evenly distributed in above-mentioned solution, suspension at this time is referred to as A；In addition 100mg AgNO is weighed at normal temperature3, make
It is dissolved in 1.5mL ethylene glycol, referred to as solution B；While stirring, solution B is instilled suspending liquid A with plastic dropper
In, 30min is stirred, temperature is risen to 155 DEG C, keeps 15min, reaction terminates；Reactant is cooled to room temperature, is centrifugated,
Washing obtains Ag/AgBr/g-C after dry3N4Nanocomposite；
(3) preparation of BiOCl (001)
Sodium chloride 146mg, enuatrol 100mg are weighed, 30mL deionized water is added, 75 DEG C of stirring 30min make enuatrol and NaCl
Sufficiently dissolution, the 0.5mol/L Bi (NO of 2mL is slowly added into round-bottomed flask3)3, and lower reaction 3 hours in 95 DEG C of degree, it will be anti-
It answers object to be cooled to room temperature, is centrifugated, washing obtains solid product after dry, which is (001) BiOCl；
(4)PVDF‐Ag/AgBr/g‐C3N4The preparation of-BiOCl (001) composite membrane
Ground BiOCl (001) powder of 5~30mg of step (3) preparation is weighed in centrifuge tube, the anhydrous second of 1~3mL is added
Alcohol；Weigh 5~30mg Ag/AgBr/g-C of step (2) preparation3N41~3mL dehydrated alcohol is added in centrifuge tube in powder；Claim
It takes 5~30mg PVDF to be placed in centrifuge tube, 1~3mL 1-Methyl-2-Pyrrolidone is added；3 centrifuge tubes are put into ultrasonic clear
It is vibrated in washing machine 5 minutes, forms suspension in two pipes, form transparence liquid in another pipe；The aluminium of clip 6cm × 6cm
Foil makes its surfacing, and four sides are turned up；Solution made of PVDF is poured into sprayer first, is then uniformly sprayed
In aluminium foil bottom surface；Similarly successively by BiOCl (001) suspension, Ag/AgBr/g-C3N4Uniform suspension is sprayed on aluminium
Foil bottom surface；It is then placed in drying in drying box, PVDF-Ag/AgBr/g-C can be obtained after 30min3N4‐BiOCl(001)
Composite membrane.
2. a kind of PVDF-Ag/AgBr/g-C as described in claim 13N4The preparation method of-BiOCl (001) composite membrane, it is special
Sign is, in the step (4): BiOCl (001), dehydrated alcohol, Ag/AgBr/g-C3N4, PVDF and 1- methyl -2- pyrrolidines
The dosage of ketone is 10mg, 2mL, 20mg, 15mg and 1mL respectively.
3. the PVDF-Ag/AgBr/g-C that preparation method as described in claim 1 obtains3N4- BiOCl (001) composite membrane is as light
Application of the catalyst in degradation methyl orange.
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|---|---|---|---|
| CN201710119934.0A CN106824271B (en) | 2017-03-02 | 2017-03-02 | A kind of PVDF-Ag/AgBr/g-C3N4The preparation method of-BiOCl (001) composite membrane |
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| CN201710119934.0A CN106824271B (en) | 2017-03-02 | 2017-03-02 | A kind of PVDF-Ag/AgBr/g-C3N4The preparation method of-BiOCl (001) composite membrane |
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| CN113546523B (en) * | 2021-07-23 | 2023-03-31 | 上海师范大学 | PVDF ultrafiltration membrane of composite Ag @ BiOBr photocatalytic material and preparation method and application thereof |
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| CN114849762B (en) * | 2022-06-14 | 2024-02-06 | 蚌埠学院 | g-C for degrading lipophilic azonaphthalene compound 3 N 4 /BiOI/Ag 2 CrO 4 Preparation method and application of ternary heterojunction photocatalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648148A (en) * | 2009-09-23 | 2010-02-17 | 合肥工业大学 | Preparation method of nanometer photocatalyst film for degrading organic matter in waste water |
| CN105709782A (en) * | 2016-03-09 | 2016-06-29 | 安徽工业大学 | Preparing method and application of Ag/AgBr/BiOCl-(001) nanometer composite material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648148A (en) * | 2009-09-23 | 2010-02-17 | 合肥工业大学 | Preparation method of nanometer photocatalyst film for degrading organic matter in waste water |
| CN105709782A (en) * | 2016-03-09 | 2016-06-29 | 安徽工业大学 | Preparing method and application of Ag/AgBr/BiOCl-(001) nanometer composite material |
Non-Patent Citations (3)
| Title |
|---|
| A plasmonic photocatalyst of Ag/AgBr nanoparticles coupled with g-C3N4 with enhanced visible-light photocatalytic ability;Yuanguo Xu et;《Colloids and Surfaces A: Physicochemical and Engineering Aspects》;20130905;第436卷;第2.3节，第3.8节第4段 * |
| Enhanced photocatalytic performance of g-C3N4 with BiOCl quantum dots modification;Chun-zhi Zheng et;《Materials Research Bulletin》;20140731;第55卷;第2.2节、第3节、第4节 * |
| 介孔氮化碳材料合成的研究进展;王悦等;《物理化学学报》;20160815;第32卷(第8期);第3节第1-2段，第4节第1、5段 * |
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