CN107519907A - A kind of carbon point and graphite phase carbon nitride composite photo-catalyst and its preparation method and application - Google Patents
A kind of carbon point and graphite phase carbon nitride composite photo-catalyst and its preparation method and application Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 33
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 23
- 239000010439 graphite Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 15
- 239000012498 ultrapure water Substances 0.000 claims abstract description 15
- 230000003115 biocidal effect Effects 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000004090 dissolution Methods 0.000 claims abstract description 11
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006471 dimerization reaction Methods 0.000 claims abstract description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000008103 glucose Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000003801 milling Methods 0.000 claims abstract description 5
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims description 46
- 229960003405 ciprofloxacin Drugs 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 15
- SPFYMRJSYKOXGV-UHFFFAOYSA-N Baytril Chemical compound C1CN(CC)CCN1C(C(=C1)F)=CC2=C1C(=O)C(C(O)=O)=CN2C1CC1 SPFYMRJSYKOXGV-UHFFFAOYSA-N 0.000 claims description 9
- 229960000740 enrofloxacin Drugs 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229960001180 norfloxacin Drugs 0.000 claims description 4
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003242 anti bacterial agent Substances 0.000 claims description 3
- 229940088710 antibiotic agent Drugs 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 3
- GSDSWSVVBLHKDQ-UHFFFAOYSA-N 9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid Chemical compound FC1=CC(C(C(C(O)=O)=C2)=O)=C3N2C(C)COC3=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-UHFFFAOYSA-N 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229960001699 ofloxacin Drugs 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000012719 thermal polymerization Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 239000013535 sea water Substances 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000006303 photolysis reaction Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- -1 river Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000006552 photochemical reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002171 ethylene diamines Chemical class 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000001055 reflectance spectroscopy Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003975 animal breeding Methods 0.000 description 1
- 239000012984 antibiotic solution Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 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
- 239000000686 essence Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- 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
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- 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
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Abstract
The present invention disclose a kind of carbon point and graphite phase carbon nitride composite photo-catalyst and its preparation method and application.This method is that glucose is added into ethylenediamine and ultra-pure water, is reacted after ultrasonic dissolution at 150~160 DEG C, treats that it is cooled to room temperature, resulting solution is centrifuged and removes bulky grain, drying obtains carbon point powder after milling；Cyanamid dimerization is added into carbon point powder and ultra-pure water again, in 450~550 DEG C of calcination reactions after being dried after ultrasonic dissolution, after it is cooled to room temperature, is milled, is sieved, obtain carbon point and graphite phase carbon nitride composite photo-catalyst.The present invention uses thermal polymerization, and synthesis technique is simple, reproducible, has the primary condition of large-scale production.Carbon point of the present invention and graphite phase carbon nitride composite photo-catalyst can be converted to the long glistening light of waves the available short wavelength light of graphite phase carbon nitride, improve the catalytic capability of graphite phase carbon nitride, and the composite photo-catalyst can degrade antibiotic under sunshine.
Description
Technical field
The invention belongs to photocatalysis technology field, is urged more particularly, to a kind of carbon point with graphite phase carbon nitride complex light
Agent and its preparation method and application.
Background technology
Antibiotic is widely used in human medical and animal-breeding, most antibiotic medicines in humans and animals body not
It can be metabolized completely, it is most of to be excreted with original shape with excrement, into environment.Antibiotic into environment can induce cause of disease
Bacterium produces drug resistance, so as to cause serious harm to the ecosystem and health.Therefore, efficient water technology pair is developed
The removal of antibiotic is significant.
In recent years, photocatalysis oxidation technique provides a new way to administer waste water, removing noxious material in environment.Stone
Black phase carbon nitride (g-C3N4) as a kind of new non-metal semiconductor materials, because its stability is high, toxicity is low and tool is visible
Photoresponse, have been widely used for photocatalysis degradation organic contaminant field.However, pure g-C3N4Still inevitably exist
Shortcoming.On the one hand, the energy gap of carbonitride is 2.7eV, the only absorbable light utilized within 475nm, to visible light utilization efficiency
It is relatively low, it is impossible to effectively to utilize solar energy.On the other hand, the photo-generated carrier recombination rate of carbonitride is higher, its catalytic activity by
To suppression, high degree limits its large-scale application.
The content of the invention
In order to solve above-mentioned the shortcomings of the prior art, there is provided a kind of carbon point and graphite phase carbon nitride complex light
The preparation method of catalyst.This method, which can obtain, possesses high visible response and the high-performance of low photo-generated carrier combined efficiency is urged
Change material, and under visible light illumination can antibiotic in efficient degradation water.
Another object of the present invention is to provide the carbon point and graphite phase carbon nitride composite photo-catalyst of above method preparation.
It is still another object of the present invention to provide the application of above-mentioned carbon point and graphite phase carbon nitride composite photo-catalyst.
The purpose of the present invention is realized by following technical proposals：
The preparation method of a kind of carbon point and graphite phase carbon nitride composite photo-catalyst, is comprised the following specific steps that：
S1. glucose is added into ethylenediamine and ultra-pure water, is reacted after ultrasonic dissolution at 150~160 DEG C, treat that it is cooled to room
Temperature, resulting solution is centrifuged and removes bulky grain, and drying obtains CDots powder after milling；
S2. cyanamid dimerization is added into CDots powder and ultra-pure water, dried after ultrasonic dissolution, in 450~500 DEG C of calcinings, treated
After it is cooled to room temperature, mill, sieve, obtain carbon point and graphite phase carbon nitride (CDots/g-C3N4) composite photo-catalyst.
Preferably, the mass volume ratio of glucose and ethylenediamine described in step S1 is (1~3)：(0.2~0.6) g/mL,
The volume ratio of the ethylenediamine and ultra-pure water is (0.2~0.6)：(10~15).
Preferably, the time reacted described in step S1 is to answer 3~5h.
Preferably, the mass ratio of cyanamid dimerization described in step S2 and carbon point powder is (1~3)：(0.01~0.1), institute
The mass volume ratio for stating carbon point powder and ultra-pure water is (0.01~0.1)：(10~15) g/mL.
Preferably, the time calcined described in step S2 is 2~3h, and the heating rate of the calcining is 2~3 DEG C/min.
A kind of CDots/g-C3N4Composite photo-catalyst is prepared by the above method.
The CDots/g-C3N4Application of the composite photo-catalyst in field of antibiotics of degrading.
Preferably, the antibiotic is Ciprofloxacin, Ofloxacin, Enrofloxacin, Norfloxacin, Metro sand star, fluorine sieve
One or more of husky star or Norfloxacin.
Above-mentioned CDots/g-C3N4The method for the application that composite photo-catalyst is degraded under simulated solar irradiation in antibiotic is such as
Under：Weigh the 0.05g composite photo-catalysts to be placed in quartzy photodissociation pipe, add the antibiotic solution that 50ml concentration is 4mg/L.Make
It is light source with 300w xenon lamps configuration 290nm optical filters.Photodissociation light such as is placed at the lower irradiation 30-60min, measured using liquid chromatogram
The amount of remaining antibiotic in solution.
Usual g-C3N4There are two defects as catalysis material：First, g-C3N4It is low to visible light utilization efficiency, it is impossible to effectively
Utilize solar energy.Another is g-C3N4Photo-generated carrier recombination rate is high in photocatalytic process, and its catalytic activity is pressed down
System.The quantum dot (CDots) that the present invention uses is the Novel Carbon Nanomaterials that a kind of size is less than 10nm.Carbon point has unique
Up-conversion luminescence function, it (550-850nm) can send short wavelength light positioned at 325-425nm under the exciting of sunshine long wave.
Therefore, carbon point has been widely used for widening the light abstraction width of catalyst in recent years.In addition, carbon point possess stronger electron storage with
Transfer ability, the compound so as to improving catalyst ability of light induced electron and hole can be suppressed.The middle CDots tools of the present invention
Standby upper conversion light function, can be converted to g-C by the long glistening light of waves3N4Available short wavelength light, solves g-C3N4The sun can not effectively be utilized
Can this drawback.Because CDots possesses very strong electron storage and transfer ability, it can conduct and store g-C3N4Photocatalytic process
In caused light induced electron, so as to suppress the compound of light induced electron and hole, improve g-C3N4Catalytic capability.
Compared with prior art, the invention has the advantages that：
1. the CDots/g-C of the present invention3N4Preparation method, using simple thermal polymerization, the letter of composite synthesis technique
It is single, it is reproducible, there is the primary condition of large-scale production, there is higher application prospect and use value.
2. the CDots/g-C of the present invention3N4CDots possesses upper conversion light function in photochemical catalyst, can be converted to the long glistening light of waves
g-C3N4Available short wavelength light, g-C can be made3N4Effectively utilize solar energy.Because CDots possesses very strong electron storage and transfer
Ability, it can conduct and store g-C3N4Caused light induced electron in photocatalytic process, so as to suppress light induced electron and hole
It is compound, improve g-C3N4Catalytic capability.
Brief description of the drawings
Fig. 1 is the CDots and CDots/g-C in embodiment 13N4TEM photos.
Fig. 2 is the g-C in comparative example 13N4TEM photos.
Fig. 3 is the fluorescence pattern of the CDots in embodiment 1.
Fig. 4 is the CDots/g-C of embodiment 13N4With the g-C in comparative example 13N4UV Diffuse Reflectance Spectroscopy.
Fig. 5 is the CDots/g-C in embodiment 13N4With the g-C in comparative example 13N4Fluorescence pattern.
Specific embodiment
Present disclosure is further illustrated with reference to specific embodiment, but should not be construed as limiting the invention.
Unless otherwise specified, the conventional meanses that technological means used in embodiment is well known to those skilled in the art.Except non-specifically
Illustrate, reagent that the present invention uses, method and apparatus is the art conventional reagent, method and apparatus.
Raw material and instrument employed in following examples are commercially available；Wherein photochemical reactor is XPA-7, and lamp source is
300w xenon lamps are simultaneously configured with 290nm optical filters, are purchased from Xujiang Electromechanical Plant, Nanjing, China.
Embodiment 1
A kind of CDots/g-C3N4The preparation of composite photo-catalyst, including step in detail below：
1. weighing 1g glucose, 0.2ml ethylenediamines and 15ml ultra-pure waters are added thereto, poly- four are transferred to after ultrasonic dissolution
With 160 DEG C of thermotonus 3h in PVF high temperature hydrothermal reaction kettle.Treat that it is cooled to room temperature, obtain brown aqueous solution, by solution
Centrifugation removes bulky grain, and drying obtains brownish black CDots powder after milling.
2. weighing 3g cyanamid dimerizations to be placed in alumina crucible, CDots powder and the 15ml for adding 0.01g thereto are ultrapure
Water, 70 DEG C of baking ovens are placed in after ultrasonic dissolution, crucible are transferred to Muffle furnace after water evaporating completely, with 3 DEG C/min heating rates
Rise to 500 DEG C and keep temperature calcination 3h.After being cooled to room temperature, mill, sieve, obtain CDots/g-C3N4Composite photocatalyst
Agent.
Comparative example 1
A kind of g-C3N4The preparation of photochemical catalyst, comprises the following steps：
Weigh 3g cyanamid dimerizations to be placed in alumina crucible, thereto 15ml ultra-pure waters, 70 DEG C of bakings are placed in after ultrasonic dissolution
Case, crucible is transferred to Muffle furnace after water evaporating completely, rising to 500 DEG C with 3 DEG C/min heating rates carries out roasting 3h.Cooling
To room temperature, mill, sieve, obtain g-C3N4Photochemical catalyst.
By CDots, CDots/g-C in embodiment 13N4With the g-C in comparative example 13N4TEM scannings are carried out respectively, are such as schemed
Shown in 1 and Fig. 2.Fig. 1 is the CDots and CDots/g-C in embodiment 13N4TEM photos.Wherein (a) be CDots, (b) be
CDots/g-C3N4.Fig. 2 is the g-C in comparative example 13N4TEM photos.From Fig. 1 and Fig. 2, CDots possesses good point
Property is dissipated, and its diameter is in 4nm or so, g-C3N4With obvious layer structure.CDots/g-C3N4In composite photo-catalyst
CDots is dispersed in g-C3N4Surface, show successfully to prepare CDots/g-C3N4Composite photo-catalyst.
Fig. 3 is the fluorescence pattern of the CDots in embodiment 1.As can be seen from Figure 3, CDots (600- in the case where long wavelength light excites
900nm) launch the light (400-600nm) of short wavelength, show that the CDots has strong up-conversion fluorescence property.Fig. 4 is embodiment
CDots/g-C in 13N4With the g-C in comparative example 13N4UV Diffuse Reflectance Spectroscopy.As shown in Figure 4, CDots/g-C3N4It is compound
The ABSORPTION EDGE of photochemical catalyst is relative to g-C3N4There occurs obvious red shift, it can thus be appreciated that CDots introducing can be improved significantly
Visible light-responded, utilization rate of the raising material to solar energy of composite.Fig. 5 is the CDots/g-C in embodiment 13N4With it is right
G-C in ratio 13N4Fluorescence pattern.The wherein a length of 350nm of excitation light wave.As shown in Figure 5, g-C is contrasted3N4, CDots/g-
C3N4Composite photo-catalyst shows weaker fluorescence intensity, shows CDots introducing and can suppress photoproduction during material light catalysis
Electronics and hole it is compound, so as to improve g-C3N4Photocatalytic activity.
Embodiment 2
A kind of CDots/g-C3N4The preparation of composite photo-catalyst, including step in detail below：
1. weighing 3g glucose, 0.6ml ethylenediamines and 10ml ultra-pure waters are added thereto, poly- four are transferred to after ultrasonic dissolution
With 150 DEG C of thermotonus 5h in PVF high temperature hydrothermal reaction kettle.Treat that it is cooled to room temperature, obtain brown aqueous solution, by solution
Centrifugation removes bulky grain, and drying obtains brownish black CDots powder after milling.
2. weighing 1g cyanamid dimerizations to be placed in alumina crucible, CDots powder and the 10ml for adding 0.1g thereto are ultrapure
Water, 70 DEG C of baking ovens are placed in after ultrasonic dissolution, crucible are transferred to Muffle furnace after water evaporating completely, with 2 DEG C/min heating rates
Rise to 450 DEG C and keep temperature calcination 2h.After being cooled to room temperature, mill, sieve, obtain CDots/g-C3N4Composite photocatalyst
Agent.
Embodiment 3
A kind of CDots/g-C3N4The application that composite photo-catalyst is handled in antibiotic waste water, comprises the following steps：
1. weighing 50mg implements CDots/g-C made from 13N4In photodissociation pipe, add 50ml concentration is composite photo-catalyst
4mg/L ciprofloxacin solution, it is placed in lucifuge in photochemical reaction instrument and adsorbs 30min.
2. carrying out light-catalyzed reaction using 300w xenon lamps configuration 290nm optical filters, surveyed after reacting 40min using liquid chromatogram
Determine the concentration C of solution residue Ciprofloxacin.According to formula N=(C0- C) * 100% calculate Ciprofloxacin clearance N, wherein C0
For the initial concentration of Ciprofloxacin.
3. weigh obtained g-C in 50mg comparative examples 13N4, repeat step 1 and 2, obtain catalyst and Ciprofloxacin gone
Except rate.
Table 1 is the CDots/g-C in embodiment 13N4With the g-C in comparative example 13N440min is reacted under simulated solar irradiation
To the degradation rate of Ciprofloxacin.As shown in Table 1, CDots/g-C3N4Clearance to Ciprofloxacin is 95.3%, compares g-C3N4Carry
It is high by 50.2%, it has been obviously improved photocatalysis efficiency.
The different catalysts system simulated solar photocatalytic degradation Ciprofloxacin of table 1
| Catalyst | g-C3N4 | CDots/g-C3N4 |
| Ciprofloxacin clearance (%) | 45.1% | 95.3% |
Embodiment 4
A kind of CDots/g-C3N4Application of the composite photo-catalyst in antibiotic waste water processing, comprises the following steps：
1. weigh CDots/g-C made from 50mg embodiments 13N4Composite photo-catalyst adds 50ml concentration in photodissociation pipe
For 4mg/L Enrofloxacin solution, it is placed in lucifuge in photochemical reaction instrument and adsorbs 30min.
2. carrying out light-catalyzed reaction using 300w xenon lamps configuration 290nm optical filters, surveyed after reacting 30min using liquid chromatogram
Determine the concentration C of solution residue Enrofloxacin.According to formula N=(C0- C) * 100% calculate Enrofloxacin clearance N, wherein C0
For the initial concentration of Ciprofloxacin.
3. weigh obtained g-C in 50mg comparative examples 13N4, repeat step 1 and 2, obtain catalyst and Enrofloxacin gone
Except rate.
Table 2 is the CDots/g-C in embodiment 13N4With the g-C in comparative example 13N430min is reacted under simulated solar irradiation
To the degradation rate table of Enrofloxacin.As shown in Table 2, CDots/g-C3N4G-C is compared to the clearance (90.7%) of Ciprofloxacin3N4
(35.5%) high, photocatalysis efficiency is significantly improved.
The different catalysts system simulated solar photocatalytic degradation Enrofloxacin of table 2
| Catalyst | g-C3N4 | CDots/g-C3N4 |
| Enrofloxacin clearance (%) | 35.5% | 90.7% |
Embodiment 5
A kind of CDots/g-C3N4Application of the composite photo-catalyst in antibiotic waste water processing, comprises the following steps：
1. the use of ultra-pure water, river, sewage effluents, seawater configuration concentration is respectively 4mg/L ciprofloxacin solutions.
2. weigh CDots/g-C made from 4 parts of 50mg embodiments 13N4Composite photo-catalyst in 4 photodissociation pipes, respectively to
The ciprofloxacin solution that 50ml steps (1) are configured wherein is added, lucifuge in photochemical reaction instrument is placed in and adsorbs 30min.
3. carrying out light-catalyzed reaction using 300w xenon lamps configuration 290nm optical filters, surveyed after reacting 40min using liquid chromatogram
Determine the concentration C of solution residue Ciprofloxacin.According to formula N=(C0- C) * 100% calculate Ciprofloxacin clearance N, wherein C0
For the initial concentration of Ciprofloxacin.Ciprofloxacin ultra-pure water, river, sewage effluents, sea water solution the clearance such as institute of table 3
Show.
Table 3 is the CDots/g-C in embodiment 13N4The photocatalysis in ultra-pure water, river, sewage effluents, sea water solution
React degradation rate tables of the 40min to Ciprofloxacin.As shown in Table 3, CDots/g-C3N4In river, sewage effluents, sea water solution
In degraded to Ciprofloxacin still keep preferable removal effect, Ciprofloxacin is in ultra-pure water, river, sewage effluents, seawater
Clearance in solution is respectively 90.7%, 86.6%, 80.3%, 82.4%.Show the CDots/g-C of the present invention3N4Complex light
The removal of catalyst antibiotic medicine suitable for actual waste water.
CDots/g-C in the water body solution of table 33N4Simulated solar photocatalytic degradation Ciprofloxacin
| Water body | Ultra-pure water | River | Sewage effluents | Seawater |
| Ciprofloxacin clearance (%) | 90.7% | 86.6% | 80.3% | 82.4% |
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine and simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (8)
1. the preparation method of a kind of carbon point and graphite phase carbon nitride composite photo-catalyst, it is characterised in that including following specific step
Suddenly：
S1. glucose is added into ethylenediamine and ultra-pure water, is reacted after ultrasonic dissolution at 150~160 DEG C, treat that it is cooled to room temperature,
Resulting solution is centrifuged and removes bulky grain, drying obtains carbon point powder after milling；
S2. cyanamid dimerization is added into carbon point powder and ultra-pure water, dried after ultrasonic dissolution, in 450~500 DEG C of calcinings, treat that its is cold
But to after room temperature, mill, sieve, obtain carbon point and graphite phase carbon nitride composite photo-catalyst.
2. the preparation method of carbon point according to claim 1 and graphite phase carbon nitride composite photo-catalyst, it is characterised in that
The mass volume ratio of glucose and ethylenediamine described in step S1 is (1~3)：(0.2~0.6) g/mL, the ethylenediamine and super
The volume ratio of pure water is (0.2~0.6)：(10~15).
3. the preparation method of carbon point according to claim 1 and graphite phase carbon nitride composite photo-catalyst, it is characterised in that
The time reacted described in step S1 is to answer 3~5h.
4. the preparation method of carbon point according to claim 1 and graphite phase carbon nitride composite photo-catalyst, it is characterised in that
The mass ratio of cyanamid dimerization described in step S2 and carbon point powder is (1~3)：(0.01~0.1), the carbon point powder and ultrapure
The mass volume ratio of water is (0.01~0.1)：(10~15) g/mL.
5. the preparation method of carbon point according to claim 1 and graphite phase carbon nitride composite photo-catalyst, it is characterised in that
The time calcined described in step S2 is 2~3h, and the heating rate of the calcining is 2~3 DEG C/min.
6. a kind of carbon point and graphite phase carbon nitride composite photo-catalyst, it is characterised in that the carbon point is answered with graphite phase carbon nitride
Closing light catalyst is prepared by any one of claim 1-5 methods described.
7. carbon point described in claim 6 and application of the graphite phase carbon nitride composite photo-catalyst in field of antibiotics of degrading.
8. carbon point according to claim 7 answering in field of antibiotics of degrading with graphite phase carbon nitride composite photo-catalyst
With, it is characterised in that the antibiotic is Ciprofloxacin, Ofloxacin, Enrofloxacin, Norfloxacin, Metro sand star, fluorine Luo Sha
One or more of star or Norfloxacin.
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