CN106881139B - A kind of CdS/Ag/g-C3N4Heterojunction composite photocatalyst and preparation method - Google Patents
A kind of CdS/Ag/g-C3N4Heterojunction composite photocatalyst and preparation method Download PDFInfo
- Publication number
- CN106881139B CN106881139B CN201710168382.2A CN201710168382A CN106881139B CN 106881139 B CN106881139 B CN 106881139B CN 201710168382 A CN201710168382 A CN 201710168382A CN 106881139 B CN106881139 B CN 106881139B
- Authority
- CN
- China
- Prior art keywords
- cds
- preparation
- reaction
- composite photocatalyst
- deionized water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 16
- 230000004044 response Effects 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 12
- 239000012265 solid product Substances 0.000 claims description 9
- 239000004201 L-cysteine Substances 0.000 claims description 8
- 235000013878 L-cysteine Nutrition 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000010944 silver (metal) Substances 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 17
- 230000015556 catabolic process Effects 0.000 abstract description 16
- 238000006731 degradation reaction Methods 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 11
- 230000003115 biocidal effect Effects 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000000356 contaminant Substances 0.000 abstract description 3
- 150000001450 anions Chemical class 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 230000005284 excitation Effects 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000004098 Tetracycline Substances 0.000 description 13
- 230000001699 photocatalysis Effects 0.000 description 13
- 229960002180 tetracycline Drugs 0.000 description 13
- 229930101283 tetracycline Natural products 0.000 description 13
- 235000019364 tetracycline Nutrition 0.000 description 13
- 150000003522 tetracyclines Chemical class 0.000 description 13
- 239000013049 sediment Substances 0.000 description 12
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 101710134784 Agnoprotein Proteins 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 229940088710 antibiotic agent Drugs 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002256 photodeposition Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 150000008538 L-cysteines Chemical class 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229960003405 ciprofloxacin Drugs 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 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
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- -1 dicyanodiamine Chemical compound 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 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
- 208000015181 infectious disease Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930000044 secondary metabolite Natural products 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- KQTXIZHBFFWWFW-UHFFFAOYSA-L silver(I) carbonate Inorganic materials [Ag]OC(=O)O[Ag] KQTXIZHBFFWWFW-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229940072172 tetracycline antibiotic Drugs 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001052 transient effect Effects 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (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 present invention provides a kind of CdS/Ag/g-C3N4Heterojunction composite photocatalyst and preparation method, steps are as follows: step 1, preparation g-C3N4Nanometer sheet；Step 2, preparation Ag/g-C3N4；Step 3, preparation CdS/Ag/g-C3N4Composite photo-catalyst.The present invention is realized with CdS/Ag/g-C3N4For the purpose of catalyst degradation antibiotic waste water.Semiconductor material is as photochemical catalyst, visible light is as excitation, special catalysis or conversion effet are realized by the interfacial interaction with contaminant molecule, the oxygen of surrounding and hydrone is set to be excited into the free anion of great oxidizing force, to harmful organic substances in the environment that achievees the purpose that degrade, the formation that this method will not result in waste of resources with additional pollution, and it is easy to operate, it is a kind of environmentally protective efficient process technology.
Description
Technical field
The invention belongs to technical field of environmental material preparation, are related to photodeposition method with hydro-thermal method and synthesize CdS/Ag/g-
C3N4The preparation method and its usage of composite photo-catalyst.
Background technique
Antibiotic (Antibiotics) class drug is primarily referred to as by some of the generations such as bacterium, mould or other microorganisms
Secondary metabolite either some artificial synthesized analogs.It is mainly used for treating various bacterium infections or pathogenic microorganisms sense
Class disease is contaminated, it is the mankind in medical science field that health and life security to the mankind, which play the role of extremely important,
One of great achievement of upper acquirement.In recent years, residual condition of the antibiotic substance in water environment is on the rise.Wherein, with four
Ring element is that the antibiotics contaminated wastewater of representative is especially pronounced, constitutes and seriously threatens to aquatic ecological and human health.Therefore,
Eliminating the environmental pollution of antibiotic residue bring and the problems such as food chain product safety in environment has been that researcher compels to be essential
The significant problem to be solved.
Photocatalysis technology has process environmental protection, easy to operate, the spies such as catalytic efficiency height as a kind of advanced oxidation technology
Point.It is well known that carrier separation efficiency can be improved in the coupling of two kinds of semiconductors.Because hetero-junctions can use two and half and lead
The energy level difference of body effectively facilitates the purpose of separation, transfer and the transmitting of electrons and holes, so as to inhibit light induced electron and sky
Cave it is compound.In recent years, Z-type hetero-junctions by researchers' extensive concern and is furtherd investigate, existing report (He J, Shao
D W,Zheng L C et al.Construction of Z-scheme Cu2O/Cu/AgBr/Ag photocatalyst
with enhanced photocatalytic activity and stability under visible
Light.Appl.Catal.B-Environ.2016,203:917-926.), by decomposition while passing through oxidation-reduction process
Sedimentation synthesizes Cu2O/Cu/AgBr/Ag Z-type is heterogeneous, effective to control the compound of electron-hole pair, improves photocatalytic activity；
(Song S Q,Meng A Y,Jiang S J et al.Construction of Z-scheme Ag2CO3/N-doped
graphene photocatalysts with enhanced visible-light photocatalytic activity
By tuning the nitrogen species.2016,396:1368-1374.), by Ag2CO3It is formed with nitrogen-doped graphene
Z-type hetero-junctions can be effectively retained the process that the strong electrons and holes of redox ability participate in degradation of contaminant, improve catalysis effect
Rate.
Polymer and graphite nitrogen carbide (g-C3N4) there is similar graphene layer structure, it is a kind of novel visible-light response type
Catalysis material.g-C3N4Synthetic method is simple, preparation cost is low, the raw materials such as melamine, dicyanodiamine, urea only pass through
Simple calcining can be obtained by the preferable g-C of catalytic performance3N4。g-C3N4Energy gap position is unique, can complete under visible light
The light-catalyzed reaction more demanding to semiconductor, but due to g-C3N4Exciton binding energy is high, crystallinity is low so that light induced electron-sky
Cave is difficult to separate, and photo-generated carrier mobility is small, causes photocatalytic process quantum efficiency relatively low.So by choosing other one
Kind semiconductor building Z-type hetero-junctions effectively inhibits Carrier recombination, improves photocatalytic activity.
CdS can directly absorb wave as a kind of most important its forbidden bandwidth of the semiconductor material about 2.4eV of II-VI group
The long visible light for being lower than 550nm, is widely used in preparing many fields such as photoelectric tube, photo resistance and solar battery.Together
When, it has fabulous photocatalysis performance, in visible light of the wavelength less than 500nm, can use CdS generate a large amount of electronics and
Redox reaction occurs for hole, and Some Organic Pollutants can be oxidized to carbon dioxide, water and inorganic salts etc..By CdS and its
He forms existing report (Huo P W, Tang Y F, the Zhou M J et al.Fabrication of of semiconductor by substance
ZnWO4-CdS heterostructure photocatalysts for visible light induced
Degradation of ciprofloxacin antibiotics.J. Ind.Eng.Chem., 2016,37:340-346), lead to
Hydro-thermal method is crossed by CdS and ZnWO4Heterojunction structure is formed, it is effective to control the compound of electron-hole pair, it is living to improve photocatalysis
Property；(Zhou P P,Le Z G,Xie Y et al.Studies on facile synthesis and properties of
mesoporous CdS/TiO2composites for photocatalysis applications.J.
Alloy.Compd., CdS and TiO 2017,692:170-177), is synthesized by simple two steps sol-gal process2It is heterogeneous to have
Effect inhibits the compound of electron-hole pair while decreasing the photoetch of CdS.To further enhance electron-transport efficiency, draw
Enter Ag particle as transmission channel, g-C can be promoted3N4The electron-transport between CdS improves photocatalytic activity.Therefore,
CdS/Ag/g-C3N4The waste water that composite photo-catalyst comes in processing environment is a kind of more satisfactory material.
Summary of the invention
The purpose of the present invention is prepare CdS/Ag/g-C using photodeposition method and hydro-thermal method as technological means3N4It is compound
Photochemical catalyst.
The present invention is achieved through the following technical solutions:
A kind of CdS/Ag/g-C3N4Heterojunction composite photocatalyst, the composite photo-catalyst are by CdS, Ag, g-C3N4
It is combined, Ag/g-C3N4Mass fraction be 20~90%, remaining is CdS；By the CdS/Ag/g-C3N4Hetero-junctions is multiple
Light combination catalyst is used for the photocatalytic degradation to tetracycline, and degradation rate has reached 85.67% in 90min.
A kind of CdS/Ag/g-C3N4The preparation method of heterojunction composite photocatalyst, steps are as follows:
Step 1, preparation g-C3N4Nanometer sheet:
Melamine is put into Muffle furnace and is calcined, wait calcine after take out grinding；Then powder is carried out again
Then calcined product is put into mechanical stirring in the beaker for filling deionized water and NaOH, is mixed by the calcining of identical program
Liquid A；Mixed liquor A is transferred to progress constant temperature thermal response in reaction kettle；After reaction, room temperature to be dropped to washs solid product,
It is dry, obtain g-C3N4Nanometer sheet；
Step 2, preparation Ag/g-C3N4:
By g-C3N4Nanometer sheet and AgNO3It is placed in deionized water and stirs to get mixed liquid B；Mixed liquid B is placed on again ultraviolet
Reaction is irradiated under lamp, after reaction, room temperature to be dropped to is dry with deionized water, ethanol washing solid product, obtains Ag/
g-C3N4, spare；
Step 3, preparation CdS/Ag/g-C3N4Composite photo-catalyst:
By CdCl22.5 and L-cysteine dissolution in deionized water and stir to being completely dissolved to obtain mixed liquor C；
The pH of mixed liquor C is adjusted with sodium hydroxide solution again, then Ag/g-C is added into mixed liquor C3N4It stirs evenly, is then added
Na2S·9H2O is simultaneously uniformly mixing to obtain mixed liquor D, then, solution is transferred to progress constant temperature thermal response in reaction kettle；Reaction
After, washing precipitate, drying obtains CdS/Ag/g-C3N4Composite photo-catalyst.
In step 1, the temperature of the calcining is gradually upgraded to 550 DEG C according to the heating rate of 2.5 DEG C/min, the reaction time
For 4h.
In step 1, when preparing mixed liquor A, used g-C3N4, NaOH and H2The amount ratio of O is 1.0g:0.40g:
90mL。
In step 1, the temperature of the constant temperature thermal response is 110 DEG C, reaction time 18h.
In step 2, the g-C3N4、AgNO3, deionized water amount ratio be 0.20g:0.01~0.07g:60ml.
In step 3, when preparing mixed liquor C, used CdCl22.5, L-cysteine, deionized water, Ag/g-
C3N4、 Na2S·9H2The amount ratio of O is 0.1833g:0.1756g:30mL:0.05~0.15g:0.045g.
In step 3, the concentration of used sodium hydroxide solution is 0.1mol/L, and pH adjusted is 5~8.
In step 3, the temperature of the constant temperature thermal response is 180 DEG C, reaction time 2h.
Prepared CdS/Ag/g-C3N4Composite photo-catalyst, for the tetracycline in degrading waste water.
Photocatalytic activity evaluation: carrying out in DW-01 type photochemical reactor (being purchased from Educational Instrument Factory, Yangzhou University), can
100mL tetracycline simulated wastewater is added in reactor and measures its initial value, composite photocatalyst is then added by light-exposed light irradiation
Agent, magnetic agitation simultaneously open aerator and are passed through air and maintain the catalyst in suspension or afloat, be spaced in During Illumination
10min sampling analysis takes supernatant liquor in spectrophotometer λ after centrifuge separationmaxAbsorbance is measured at=358nm, and is passed through
Formula: DR=[(A0-Ai)/A0] × 100% calculates degradation rate, wherein A0The extinction of tetracycline when to reach adsorption equilibrium
Degree, AiFor the absorbance of the tetracycline of timing sampling measurement.
Melamine used in the present invention, silver nitrate, sodium hydroxide, caddy, L-cysteine salt are that analysis is pure,
It is purchased from traditional Chinese medicines chemical reagent Co., Ltd；Tetracycline antibiotic is mark product, is purchased from Shanghai along vigorous bioengineering Co., Ltd.
The utility model has the advantages that
The present invention is realized with CdS/Ag/g-C3N4For the purpose of catalyst degradation antibiotic waste water.Semiconductor material conduct
Photochemical catalyst, it is seen that light realizes that special catalysis or conversion are imitated as excitation, by the interfacial interaction with contaminant molecule
It answers, the oxygen of surrounding and hydrone is made to be excited into the free anion of great oxidizing force, so that reaching nocuousness in degradation environment has
The purpose of machine substance, the formation that this method will not result in waste of resources with additional pollution, and it is easy to operate, it is a kind of environmentally protective
Efficient process technology.
Detailed description of the invention
Fig. 1 is CdS/Ag/g-C3N4Composite photo-catalyst fluorogram is schemed (b) wherein figure (a) is Solid fluorescene spectrum
For transient state fluorescence spectrum；
Fig. 2 is CdS/Ag/g-C3N4The TEM of composite photo-catalyst schemes；
Fig. 3 is CdS/Ag/g-C3N4The photoelectricity flow graph of composite photo-catalyst.
Specific embodiment
Below with reference to specific implementation example, the present invention will be further described.
Embodiment 1:
(1)g-C3N4The preparation of nanometer sheet:
5g melamine is calcined, moves to and calcines 4h in 550 DEG C of Muffle furnaces, heating rate is 2.5 DEG C/min.Wait forge
Grinding is taken out after burning；Then calcining that powder is carried out to identical program again, obtains g-C3N4Nanometer sheet.Then by the g- of 1g
C3N4Nanometer sheet is put into equipped with 90cm3Mechanical stirring 30min in the beaker of deionized water and 0.40g NaOH；Then, solution is turned
Move to progress 18h constant temperature thermal response in 110 DEG C of reaction kettles；After reaction, room temperature to be dropped to, with deionized water, ethanol washing
Solid product, it is dry, obtain g-C3N4Nanometer sheet.
(2)Ag/g-C3N4Preparation:
By the g-C of 0.20g3N4Nanometer sheet and 0.05g AgNO3It is dissolved in 60ml deionized water and stirs；Solution is put again
Irradiation 3h restores AgNO in the UV lamp3, after reaction, room temperature to be dropped to, with deionized water, ethanol washing solid product,
It is dry, obtain Ag/g-C3N4, spare；
(3)CdS/Ag/g-C3N4The preparation of composite photo-catalyst:
By 0.1833g CdCl22.5 and 0.1756g L-cysteine is dissolved in 30mL deionized water and stirs extremely
It is completely dissolved；0.1mol L is used again-1Sodium hydroxide solution adjusts the pH=7 of above-mentioned solution, then 0.1g Ag/g- is wherein added
C3N4Continue to stir evenly, 0.045g Na is then added2S·9H2O is simultaneously stirred evenly, and then, solution is transferred to 180 DEG C instead
Answer progress 2h constant temperature thermal response in kettle；After reaction, sediment is separated with solution with magnet, with ethanol washing sediment,
It is put into vacuum oven and dries, obtain CdS/Ag/g-C3N4Composite photo-catalyst.
(4) it takes sample in (3) to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to Fourth Ring
The degradation rate of plain antibiotic reaches 85.67% in 90min.
Embodiment 2:
By the step in embodiment 1, unlike (2) by the g-C of 0.20g3N4Nanometer sheet and 0.01g AgNO3It is dissolved in
It is stirred in 60ml deionized water；Solution is put into irradiation 3h reduction AgNO in the UV lamp again3, after reaction, room to be dropped to
Temperature, it is dry with deionized water, ethanol washing solid product, obtain Ag/g-C3N4。
It takes sample in (2) to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to tetracycline
Degradation rate reach 30.56% in 90min.
Embodiment 3:
By the step in embodiment 1, unlike (2) by the g-C of 0.20g3N4Nanometer sheet and 0.03g AgNO3It is dissolved in
It is stirred in 60ml deionized water；Solution is put into irradiation 3h reduction AgNO in the UV lamp again3, after reaction, room to be dropped to
Temperature, it is dry with deionized water, ethanol washing solid product, obtain Ag/g-C3N4。
It takes sample in (2) to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to tetracycline
Degradation rate reach 50.41% in 90min.
Embodiment 4:
By the step in embodiment 1, unlike (2) by the g-C of 0.20g3N4Nanometer sheet and 0.07g AgNO3It is dissolved in
It is stirred in 60ml deionized water；Solution is put into irradiation 3h reduction AgNO in the UV lamp again3, after reaction, room to be dropped to
Temperature, it is dry with deionized water, ethanol washing solid product, obtain Ag/g-C3N4。
It takes sample in (2) to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to tetracycline
Degradation rate reach 40.83% in 90min.
Embodiment 5:
By the step in embodiment 1, unlike (3) by 0.1833g CdCl22.5 and 0.1756g L-cysteine
It is dissolved in 30 mL deionized waters and stirs to being completely dissolved；0.1mol L is used again-1Sodium hydroxide solution adjusts above-mentioned solution
PH=5, then 0.1g Ag/g-C is wherein added3N4Continue to stir evenly, 0.045g Na is then added2S·9H2O is simultaneously stirred equal
It is even, then, solution is transferred to progress 2h constant temperature thermal response in 180 DEG C of reaction kettles；After reaction, with magnet by sediment with
Solution separation, with ethanol washing sediment, is put into vacuum oven and dries, obtain CdS/Ag/g-C3N4Composite photo-catalyst.
It takes sample in (3) to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to tetracycline
Degradation rate reach 52.72% in 90min.
Embodiment 6:
By the step in embodiment 1, unlike (3) by 0.1833g CdCl22.5 and 0.1756g L-cysteine
It is dissolved in 30 mL deionized waters and stirs to being completely dissolved；0.1mol L is used again-1Sodium hydroxide solution adjusts above-mentioned solution
PH=6, then 0.1g Ag/g-C is wherein added3N4Continue to stir evenly, 0.045g Na is then added2S·9H2O is simultaneously stirred equal
It is even, then, solution is transferred to progress 2h constant temperature thermal response in 180 DEG C of reaction kettles；After reaction, with magnet by sediment with
Solution separation, with ethanol washing sediment, is put into vacuum oven and dries, obtain CdS/Ag/g-C3N4Composite photo-catalyst.
It takes sample in (3) to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to tetracycline
Degradation rate reach 56.37% in 90min.
Embodiment 7:
By the step in embodiment 1, unlike (3) by 0.1833g CdCl22.5 and 0.1756g L-cysteine
It is dissolved in 30 mL deionized waters and stirs to being completely dissolved；0.1mol L is used again-1Sodium hydroxide solution adjusts above-mentioned solution
PH=8, then 0.1g Ag/g-C is wherein added3N4Continue to stir evenly, 0.045g Na is then added2S·9H2O is simultaneously stirred equal
It is even, then, solution is transferred to progress 2h constant temperature thermal response in 180 DEG C of reaction kettles；After reaction, with magnet by sediment with
Solution separation, with ethanol washing sediment, is put into vacuum oven and dries, obtain CdS/Ag/g-C3N4Composite photo-catalyst.
It takes sample in (3) to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to tetracycline
Degradation rate reach 55.61% in 90min.
Embodiment 8:
By 0.1833g CdCl22.5 and 0.1756g L-cysteine is dissolved in 30mL deionized water and stirs extremely
It is completely dissolved；0.1mol L is used again-1Sodium hydroxide solution adjusts the pH=7 of above-mentioned solution, then 0.05g Ag/g- is wherein added
C3N4Continue to stir evenly, 0.045g Na is then added2S·9H2O is simultaneously stirred evenly, and then, solution is transferred to 180 DEG C instead
Answer progress 2h constant temperature thermal response in kettle；After reaction, sediment is separated with solution with magnet, with ethanol washing sediment,
It is put into vacuum oven and dries, obtain CdS/Ag/g-C3N4Composite photo-catalyst.
It takes sample in (3) to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to tetracycline
The degradation rate of antibiotic reaches 71.67% in 90min.
Embodiment 9:
By 0.1833g CdCl22.5 and 0.1756g L-cysteine is dissolved in 30mL deionized water and stirs extremely
It is completely dissolved；0.1mol L is used again-1Sodium hydroxide solution adjusts the pH=7 of above-mentioned solution, then 0.15g Ag/g- is wherein added
C3N4Continue to stir evenly, 0.045g Na is then added2S·9H2O is simultaneously stirred evenly, and then, solution is transferred to 180 DEG C instead
Answer progress 2h constant temperature thermal response in kettle；After reaction, sediment is separated with solution with magnet, with ethanol washing sediment,
It is put into vacuum oven and dries, obtain CdS/Ag/g-C3N4Composite photo-catalyst.
It takes sample in (3) to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to tetracycline
The degradation rate of antibiotic reaches 81.76% in 90min.
About characterization of the invention, Fig. 1 CdS/Ag/g-C3N4Composite photo-catalyst photocatalysis fluorogram；It is very clear in figure
Chu presents CdS/Ag/g-C3N4With good catalytic activity.Fig. 2 is CdS/Ag/g-C3N4The TEM of composite photo-catalyst
Figure；As can be seen from the figure photochemical catalyst has good structure.Fig. 3 is CdS/Ag/g-C3N4The photoelectric current of composite photo-catalyst
Figure.As can be seen from the figure CdS/Ag/g-C3N4With excellent photocatalytic activity.
Claims (8)
1. a kind of CdS/Ag/g-C3N4The preparation method of heterojunction composite photocatalyst, which is characterized in that steps are as follows:
Step 1, preparation g-C3N4Nanometer sheet:
Melamine is put into Muffle furnace and is calcined, wait calcine after take out grinding；Then powder is carried out again identical
Then calcined product is put into mechanical stirring in the beaker for filling deionized water and NaOH, obtains mixed liquor A by the calcining of program；
Mixed liquor A is transferred to progress constant temperature thermal response in reaction kettle；After reaction, room temperature to be dropped to washs solid product, does
It is dry, obtain g-C3N4Nanometer sheet；
Step 2, preparation Ag/g-C3N4:
By g-C3N4Nanometer sheet and AgNO3It is placed in deionized water and stirs to get mixed liquid B；Mixed liquid B is put in the UV lamp again
Irradiation reaction, after reaction, room temperature to be dropped to are dry with deionized water, ethanol washing solid product, obtain Ag/g-C3N4,
It is spare；
Step 3, preparation CdS/Ag/g-C3N4Composite photo-catalyst:
By CdCl2·2.5H2O and L-cysteine dissolution in deionized water and are stirred to being completely dissolved to obtain mixed liquor C；Again
The pH of mixed liquor C is adjusted with sodium hydroxide solution, then Ag/g-C is added into mixed liquor C3N4It stirs evenly, is then added
Na2S·9H2O is simultaneously uniformly mixing to obtain mixed liquor D, then, solution is transferred to progress constant temperature thermal response in reaction kettle；Reaction knot
Shu Hou, washing precipitate, drying obtain CdS/Ag/g-C3N4Composite photo-catalyst.
2. a kind of CdS/Ag/g-C as described in claim 13N4The preparation method of heterojunction composite photocatalyst, feature exist
In in step 1, the temperature of the calcining is gradually upgraded to 550 DEG C according to the heating rate of 2.5 DEG C/min, reaction time 4h.
3. a kind of CdS/Ag/g-C as described in claim 13N4The preparation method of heterojunction composite photocatalyst, feature exist
In, in step 1, when preparing mixed liquor A, used g-C3N4, NaOH and H2The amount ratio of O is 1.0g:0.40g:90mL.
4. a kind of CdS/Ag/g-C as described in claim 13N4The preparation method of heterojunction composite photocatalyst, feature exist
In in step 1, the temperature of the constant temperature thermal response is 110 DEG C, reaction time 18h.
5. a kind of CdS/Ag/g-C as described in claim 13N4The preparation method of heterojunction composite photocatalyst, feature exist
In, in step 2, the g-C3N4、AgNO3, deionized water amount ratio be 0.20g:0.01~0.07g:60ml.
6. a kind of CdS/Ag/g-C as described in claim 13N4The preparation method of heterojunction composite photocatalyst, feature exist
In, in step 3, used CdCl2·2.5H2O, L-cysteine, deionized water, Ag/g-C3N4、Na2S·9H2The dosage of O
Than for 0.1833g:0.1756g:30mL:0.05~0.15g:0.045g.
7. a kind of CdS/Ag/g-C as described in claim 13N4The preparation method of heterojunction composite photocatalyst, feature exist
In in step 3, the concentration of used sodium hydroxide solution is 0.1mol/L, and pH adjusted is 5~8.
8. a kind of CdS/Ag/g-C as described in claim 13N4The preparation method of heterojunction composite photocatalyst, feature exist
In in step 3, the temperature of the constant temperature thermal response is 180 DEG C, reaction time 2h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710168382.2A CN106881139B (en) | 2017-03-21 | 2017-03-21 | A kind of CdS/Ag/g-C3N4Heterojunction composite photocatalyst and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710168382.2A CN106881139B (en) | 2017-03-21 | 2017-03-21 | A kind of CdS/Ag/g-C3N4Heterojunction composite photocatalyst and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106881139A CN106881139A (en) | 2017-06-23 |
| CN106881139B true CN106881139B (en) | 2019-08-27 |
Family
ID=59180904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710168382.2A Active CN106881139B (en) | 2017-03-21 | 2017-03-21 | A kind of CdS/Ag/g-C3N4Heterojunction composite photocatalyst and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106881139B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108404959B (en) * | 2018-03-09 | 2021-01-12 | 台州职业技术学院 | Rod-like g-C3N4@SnIn4S8Composite photocatalyst and preparation method thereof |
| CN108636436A (en) * | 2018-04-28 | 2018-10-12 | 西安工程大学 | Effectively construct the preparation method of Z-type ternary heterojunction photochemical catalyst |
| CN109225303A (en) * | 2018-10-23 | 2019-01-18 | 江苏大学 | A kind of dimensional thinlayer Au/g-C3N4The Preparation method and use of composite photo-catalyst |
| CN110075896B (en) * | 2019-04-09 | 2021-12-07 | 重庆大学 | FeS2/g-C3N4Preparation method and application of heterojunction material |
| CN110420645A (en) * | 2019-07-29 | 2019-11-08 | 西安工程大学 | A kind of photochemical catalyst preparation method with adsorptivity and photocatalysis performance |
| CN110560188B (en) * | 2019-09-19 | 2021-09-28 | 济南大学 | Preparation method of multi-stage sample injection micro-fluidic chip for synthesizing Ag/Ag2S/CdS heterojunction |
-
2017
- 2017-03-21 CN CN201710168382.2A patent/CN106881139B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| Activation of graphitic carbon nitride (g-C3N4) by alkaline hydrothermal treatment for photocatalytic NO oxidation in gas phase;Taizo Sano,et.al.;《Journal of Materials Chemistry A》;20130403;第6489–6496页 * |
| Enhanced photocatalytic H2 evolution over CdS/Au/g-C3N4 composite photocatalyst under visible-light irradiation;Xiaoling Ding,et.al.;《APL MATERIALS》;20151031;第3卷;第104410-1到104410-7页 * |
| Photochemical preparation of the ternary composite CdS/Au/g-C3N4 with enhanced visible light photocatalytic performance and its microstructure;Daluo Peng,et.al.;《RSC Adv.》;20160810;第6卷;摘要，第77761页第2.2节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106881139A (en) | 2017-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106881139B (en) | A kind of CdS/Ag/g-C3N4Heterojunction composite photocatalyst and preparation method | |
| CN106975507A (en) | A kind of Ag/g C3N4Composite photo-catalyst and preparation method thereof | |
| CN105170170B (en) | A kind of g C3N4 ZnO/HNTs composite photo-catalysts and preparation method thereof and purposes | |
| CN110180548A (en) | Empty nanotube/two dimension zinc ferrite nanometer sheet heterojunction composite and its application in removal water pollutant in one-dimensional indium oxide | |
| Gao et al. | A review on mechanism, applications and influencing factors of carbon quantum dots based photocatalysis | |
| CN103506136B (en) | A kind of CdS/WO 3the preparation method of composite photo-catalyst and application thereof | |
| CN104353469A (en) | Method for preparing nanocomposite photocatalyst and application of nanocomposite photocatalyst | |
| CN103506139A (en) | Preparation method and application of hydrothermal synthesized CdSe quantum dot photocatalyst | |
| Graimed et al. | Highly stable β-Bi2O3/Ag decorated nanosilica as an efficient Schottky heterojunction for ciprofloxacin photodegradation in wastewater under LED illumination | |
| CN107029771B (en) | Silver carbonate/silver/tungstic acid tri compound Z-type photochemical catalyst and its preparation method and application | |
| CN106540717A (en) | A kind of hydro-thermal method synthesizes recyclable CdS/CoFe2O4The preparation method and its usage of/rGO composite photo-catalysts | |
| CN103623847B (en) | A kind of CdSe-Bi 2wO 6the preparation method of photochemical catalyst | |
| Raja et al. | Direct Z-scheme ZnIn2S4 spheres and CeO2 nanorods decorated on reduced-graphene-oxide heterojunction photocatalysts for hydrogen evolution and photocatalytic degradation | |
| CN106044842B (en) | A kind of preparation method and applications of fan-shaped hydroxyl zinc fluoride | |
| CN106513018B (en) | A kind of core-shell structure ZnFe2O4The preparation method and its usage of@CdS composite photo-catalyst | |
| CN109126854A (en) | A kind of CdS/g-C3N4The preparation method of double nano piece composite photo-catalyst | |
| CN103316692A (en) | Preparation method and application of CdS/CNTs composite photocatalyst | |
| CN107890877A (en) | A kind of Bi3O4Cl/CdS composites and preparation method and purposes | |
| CN107442153A (en) | A kind of g C based on the modification of waste paper biomass carbon3N4The Preparation method and use of composite photo-catalyst | |
| CN106552651A (en) | A kind of Bi12O17Br2The synthesis of photochemical catalyst and application process | |
| CN105728008A (en) | Method for preparing AgCl/Bi2O2CO3 composite photocatalytic material and product of material | |
| CN107790156B (en) | A kind of preparation and its application of t-Se stick load BiOCl superthin section composite photo-catalyst | |
| CN109675547A (en) | A kind of preparation method and applications of hollow cube type zinc stannate photochemical catalyst | |
| CN105056986A (en) | Method for preparing flake shaped bismuth oxide nitrate hydroxide photocatalyst and catalyst application | |
| CN108940349A (en) | The method of carbonitride Z-type photochemical catalyst removal dyestuff contaminant is mixed using siliver chromate/sulphur |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201103 Address after: No.18 Renmin Road, Qindong Town, Dongtai City, Yancheng City, Jiangsu Province, 224000 Patentee after: Dongtai Qindong Technology Development Co., Ltd Patentee after: JIANGSU University Address before: Zhenjiang City, Jiangsu Province, 212013 Jingkou District Road No. 301 Patentee before: JIANGSU University |