CN109603882A - Utilize the method for modified carbon quantum dot load hollow tubular carbon nitride photocatalyst processing organic pollutant and photo-catalyst - Google Patents
Utilize the method for modified carbon quantum dot load hollow tubular carbon nitride photocatalyst processing organic pollutant and photo-catalyst Download PDFInfo
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- CN109603882A CN109603882A CN201811601178.6A CN201811601178A CN109603882A CN 109603882 A CN109603882 A CN 109603882A CN 201811601178 A CN201811601178 A CN 201811601178A CN 109603882 A CN109603882 A CN 109603882A
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 84
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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
- 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
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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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical 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
- 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
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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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Abstract
The invention discloses a kind of methods using modified carbon quantum dot load hollow tubular carbon nitride photocatalyst processing organic pollutant and photo-catalyst, photocatalysis treatment is carried out method includes the following steps: modified carbon quantum dot load hollow tubular carbon nitride photocatalyst is mixed with organic pollutant wastewater or bacterial solution, complete the processing to organic pollutant or bacterium, wherein being modified carbon quantum dot load hollow tubular carbon nitride photocatalyst is using hollow tubular carbonitride as carrier, load has modified carbon quantum dot thereon, hollow tubular carbonitride be using molar ratio be 1~5: 1 urea and melamine be prepared by hydro-thermal and calcining as raw material.The method that the present invention handles organic pollutant and photo-catalyst have many advantages, such as simple process, easy to operate, equipment is simple, low in cost, treatment effeciency it is high/photocatalysis efficiency is high, removal effect it is good/bactericidal effect is good, cleanliness without any pollution, with very high application value and commercial value.
Description
Technical field
The invention belongs to visible light catalytic fields, are related to a kind of utilize and are modified carbon quantum dot load hollow tubular carbonitride light
The method of catalyst treatment organic pollutant and photo-catalyst.
Background technique
The fast development of the rapid growth and economy of population is so that demand of the mankind to water resource increasingly increases, thus
Bring water pollution problems is global problem, and wherein organic pollutant pollution problem caused by water environment, extensive
Concern, if antibiotic waste water is as used water difficult to degradate, has been a hot spot of research.Antibiotic is due to antibacterial, antimycotic, anti-
The characteristics such as virus, anti parasitic have a wide range of applications in medicine and aquaculture.Tetracycline (TC) as antibiotic one
Kind, a kind of essential drugs are considered as by the World Health Organization (WHO).However, the intracorporal TC metabolism of animal is poor, lead to a large amount of medicine
The metabolite of object precursor or TC enter water environment.According to previous report, in sanitary sewage the concentration range of antibiotic from
100ng/L to 6mg/L, these contaminated water bodys seriously endanger human health.In addition, the biohazard such as bacterium, virus, fungi
Substance is widely present in drinking water (surface water, underground water), they constitute significant threat to human health, to aquatic ecological
System also results in adverse effect.For example, Escherichia coli can cause a variety of intestines problems as a kind of invasive organism.
The problems such as in order to solve above-mentioned organic pollutant wastewater and bacterium, researcher's applied chemistry flocculence, biomembrane
The methods of filtration method, physisorphtion, ultraviolet lighting, however these methods are extremely difficult to ideal treatment effect, thus seek
A kind of simple and easy method is looked for carry out effective degradable organic pollutant and kill bacterium tool to have very important significance.In recent years, light
Catalysis technique has received widespread attention as a kind of environmental-friendly, efficient, inexpensive technology.However, traditional photocatalysis
Agent such as TiO2And ZnO, since the forbidden band of itself is wider, to ultraviolet light can only be absorbed and sunlight cannot be utilized well.
Graphite type carbon nitride (g-C3N4) it is used as a kind of conjugated polymer semiconductor, sizable concern is caused recently, because
There is good physical and chemical stability, attractive electronic structure and band gap appropriate for it, i.e. 2.7eV is being catalyzed
It has a good application prospect in terms of the energy.But that there is also specific surface areas is small simultaneously, exciton binding energy is high, light induced electron is empty for it
The compound intrinsic problem such as serious in cave, causes its photocatalysis efficiency lower, this seriously restricts it in the energy and environmental photocatlytsis field
Practical application and popularization.The nanostructure of photochemical catalyst and its physicochemical properties and photocatalysis performance exist closely
Connection, when the scale of semiconductor material narrows down to nanometer range, will show unique skin effect, small-size effect and
Quantum size effect, and the synergistic effect of these effects will significantly improve the photocatalysis performance of nano material.Nano wire, nanometer rods
Equal monodimension nanometer materials are because of performances such as its novel optics, electricity, magnetics, mechanics, in many necks such as nano-device and photocatalysis
Domain views go out potential application prospect.However, the carbon nitride photocatalyst of existing different-shape still has, specific surface area is small, lives
Property site is few, the compound serious, disadvantages such as absorbing ability is poor, photocatalytic activity is low of photo-generated carrier.In addition, existing carbonitride light is urged
Most of preparation process of agent is template, needs to be removed template in their synthesis process, this is unfavorable for improving
Preparation efficiency, and cause preparation process complexity, preparation cost higher, it takes time and effort, while these synthesis technologies needs make extensively
With various organic material additives or condition of high voltage, wherein organic additive is generally difficult to completely remove, and residual quantity not only can
The photocatalysis performance of carbon nitride photocatalyst is influenced, and these organic additives are also possible to that environment can be adversely affected, this
The presence of a little problems seriously limits the extensive use of carbon nitride photocatalyst.Therefore, a kind of large specific surface area, hole number are obtained
Measure the modification carbon amounts that more, active site is more, photo-generated carrier separates and migration rate is fast, absorbing ability is strong, photocatalytic activity is high
Son point load hollow tubular carbon nitride photocatalyst and the synthesis that matches therewith it is convenient, it is easy to operate, to environment without secondary dirt
The preparation method of the modification carbon quantum dot load hollow tubular carbon nitride photocatalyst of dye, it is organic in environment for effectively removing
Pollutant and harmful microorganism have a very important significance.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, provide a kind of simple process, it is easy to operate,
Equipment is simple, low in cost, treatment effeciency is high, removal effect is good, cleanliness without any pollution hollow using modified carbon quantum dot load
The method that tubulose carbon nitride photocatalyst handles organic pollutant, additionally provides that a kind of simple process, easy to operate, equipment is simple
It is single, low in cost, photocatalysis efficiency is high, bactericidal effect is good, cleanliness without any pollution loads hollow tubular using modified carbon quantum dot
The method of carbon nitride photocatalyst photo-catalyst.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A method of organic pollutant, packet are handled using modified carbon quantum dot load hollow tubular carbon nitride photocatalyst
It includes following steps: modified carbon quantum dot load hollow tubular carbon nitride photocatalyst being mixed with organic pollutant wastewater, is reached
Photocatalytic degradation reaction is carried out after adsorption equilibrium, completes the processing to organic pollutant；The modified carbon quantum dot load is hollow
Tubulose carbon nitride photocatalyst is using hollow tubular carbonitride as carrier, and load has modified carbon amounts on the hollow tubular carbonitride
Sub- point；The hollow tubular carbonitride is to be prepared using urea and melamine as raw material by hydro-thermal and calcining；The urine
The molar ratio of element and melamine is 1~5: 1.
Above-mentioned method, it is further improved, the modified carbon quantum dot load hollow tubular carbon nitride photocatalyst with
Organic pollutant wastewater ratio is 20mg~30mg: 30mL；The organic pollutant wastewater is antibiotic waste water；The antibiotic
Antibiotic in waste water is tetracycline and/or sulfamethazine etc.；The concentration of antibiotic in the antibiotic waste water≤
20mg/L；Described be mixed into is stirred under dark condition；The revolving speed of the stirring is 400r/min；The time of the stirring
For 60min；The photocatalytic degradation reaction carries out under illumination condition；The light source of the illumination condition is the xenon lamp of 300W；Institute
The time for stating photocatalytic degradation reaction is 1h~2h.
Above-mentioned method, it is further improved, the modified carbon quantum dot load hollow tubular carbon nitride photocatalyst
The following steps are included: hollow tubular carbonitride is suspended in water, addition carbon modified quantum dot solution, drying obtains preparation method
Hollow tubular carbon nitride photocatalyst is loaded to modified carbon quantum dot.
Above-mentioned method, it is further improved, the preparation method of the hollow tubular carbonitride the following steps are included:
S1, urea and melamine are dissolved in solvent, ultrasound, stirring obtains mixed solution；
S2, mixed solution obtained in step S1 is subjected to hydro-thermal reaction, cleaned, filtered, it is dry, obtain presoma；
S3, presoma obtained in step S2 is calcined, grinds, obtains hollow tubular carbonitride.
Above-mentioned method, further improved, in the step S1, the molar ratio of the urea and melamine is 1~5
:1；The solvent is water；The time of the ultrasound is 0.5h~3h, and the time of the stirring is 8h~18h；
In the step S2, temperature >=180 DEG C of the hydro-thermal reaction；The time of the hydro-thermal reaction is for 24 hours~36h；
The temperature of the drying is 60 DEG C~85 DEG C；The time of the drying is 8h~12h；
In the step S3, heating rate is 2.3 DEG C/min~5 DEG C/min in the calcination process；The temperature of the calcining
Degree is 550 DEG C~650 DEG C；The time of the calcining is 4h~6h.
Above-mentioned method, it is further improved, the preparation method of the carbon modified quantum dot solution the following steps are included:
(1) sodium citrate and cysteine are dissolved in solvent, stir, obtains precursor solution；
(2) precursor solution obtained in step (1) is subjected to hydro-thermal reaction, dialysis obtains carbon modified quantum dot solution.
Above-mentioned method, it is further improved, in the step (1), the molar ratio of the sodium citrate and cysteine
It is 1: 1；The solvent is water；The revolving speed of the stirring is 300r/min~500r/min；The time of the stirring is 1h~2h；
In the step (2), the temperature of the hydro-thermal reaction is 180 DEG C~220 DEG C；The time of the hydro-thermal reaction is 6h
~8h；The time of the dialysis is 12h~for 24 hours.
Above-mentioned method, it is further improved, the ratio of the hollow tubular carbonitride and water is 0.2g: 30mL~
50mL；The ratio of the hollow tubular carbonitride and carbon modified quantum dot solution is 0.2g: 0.5mL~3mL；The modified carbon amounts
The concentration of son point solution is 1mg/mL；The temperature of the drying is 70 DEG C~80 DEG C；The time of the drying is 18h~for 24 hours.
As a general technical idea, hollow tubular nitrogen is loaded using modified carbon quantum dot the present invention also provides a kind of
Change the method for carbon photochemical catalyst photo-catalyst, comprising the following steps: modified carbon quantum dot is loaded into hollow tubular carbonitride light
Catalyst mixes progress photo-catalyst with bacterial solution and reacts, and completes the inactivation to bacterium；The modified carbon quantum dot load
Hollow tubular carbon nitride photocatalyst is using hollow tubular carbonitride as carrier, and load has modification on the hollow tubular carbonitride
Carbon quantum dot；The hollow tubular carbonitride is to be prepared using urea and melamine as raw material by hydro-thermal and calcining；Institute
The molar ratio for stating urea and melamine is 1~5: 1.
Above-mentioned method, it is further improved, the modified carbon quantum dot load hollow tubular carbon nitride photocatalyst with
Bacterial solution ratio is 20mg~30mg: 0.5mL；Bacterium in the bacterial solution is Escherichia coli and/or golden staphylococci；
Concentration≤3 × 10 of bacterium in the bacterial solution9CFU/mL；The photo-catalyst reaction carries out under illumination condition；Institute
The light source for stating illumination condition is the xenon lamp of 300W；The time of the photo-catalyst reaction is 1h~2h.
Above-mentioned method, it is further improved, the modified carbon quantum dot load hollow tubular carbon nitride photocatalyst
The following steps are included: hollow tubular carbonitride is suspended in water, addition carbon modified quantum dot solution, drying obtains preparation method
Hollow tubular carbon nitride photocatalyst is loaded to modified carbon quantum dot.
Above-mentioned method, it is further improved, the preparation method of the hollow tubular carbonitride the following steps are included:
S1, urea and melamine are dissolved in solvent, ultrasound, stirring obtains mixed solution；
S2, mixed solution obtained in step S1 is subjected to hydro-thermal reaction, cleaned, filtered, it is dry, obtain presoma；
S3, presoma obtained in step S2 is calcined, grinds, obtains hollow tubular carbonitride.
Above-mentioned method, further improved, in the step S1, the molar ratio of the urea and melamine is 1~5
:1；The solvent is water；The time of the ultrasound is 0.5h~3h, and the time of the stirring is 8h~18h；
In the step S2, temperature >=180 DEG C of the hydro-thermal reaction；The time of the hydro-thermal reaction is for 24 hours~36h；
The temperature of the drying is 60 DEG C~85 DEG C；The time of the drying is 8h~12h；
In the step S3, heating rate is 2.3 DEG C/min~5 DEG C/min in the calcination process；The temperature of the calcining
Degree is 550 DEG C~650 DEG C；The time of the calcining is 4h~6h.
Above-mentioned method, it is further improved, the preparation method of the carbon modified quantum dot solution the following steps are included:
(1) sodium citrate and cysteine are dissolved in solvent, stir, obtains precursor solution；
(2) precursor solution obtained in step (1) is subjected to hydro-thermal reaction, dialysis obtains carbon modified quantum dot solution.
Above-mentioned method, it is further improved, in the step (1), the molar ratio of the sodium citrate and cysteine
It is 1: 1；The solvent is water；The revolving speed of the stirring is 300r/min~500r/min；The time of the stirring is 1h~2h；
In the step (2), the temperature of the hydro-thermal reaction is 180 DEG C~220 DEG C；The time of the hydro-thermal reaction is 6h
~8h；The time of the dialysis is 12h~for 24 hours.
Above-mentioned method, it is further improved, the ratio of the hollow tubular carbonitride and water is 0.2g: 30mL~
50mL；The ratio of the hollow tubular carbonitride and carbon modified quantum dot solution is 0.2g: 0.5mL~3mL；The modified carbon amounts
The concentration of son point solution is 1mg/mL；The temperature of the drying is 70 DEG C~80 DEG C；The time of the drying is 18h~for 24 hours.
Compared with the prior art, the advantages of the present invention are as follows:
(1) it is organic using modified carbon quantum dot load hollow tubular carbon nitride photocatalyst processing that the present invention provides a kind of
The method of pollutant is mixed by that will be modified carbon quantum dot load hollow tubular carbon nitride photocatalyst with organic pollutant wastewater
Photocatalytic degradation reaction is carried out, the efficient degradation to organic pollutant can be realized, there is simple process, easy to operate, equipment
Simply, low in cost, the advantages that treatment effeciency is high, removal effect is good, cleanliness without any pollution, may be widely used in removal water body
Organic pollutant (such as antibiotic), have very high application value and commercial value.By taking tetracycline as an example, using modified carbon amounts
Son point load hollow tubular carbon nitride photocatalyst photocatalytic degradation reacts 60min, is up to the degradation rate of tetracycline
82.67%, the efficient removal to tetracycline is realized, meanwhile, degradation removal rate is still up to 79.87% after circulation four times, only
The degradation rate of loss 2.8%, can satisfy practical application request.
(2) photocatalysis of hollow tubular carbon nitride photocatalyst is loaded using modified carbon quantum dot the present invention also provides a kind of
The method of sterilization loads hollow tubular carbon nitride photocatalyst and mixes with bacterial solution progress light by will be modified carbon quantum dot and urges
Change bactericidal reaction, can in a relatively short period of time quickly, be thoroughly catalyzed inactivation of bacterial, realize to the efficient inactivation of bacterium, tool
Have that simple process, easy to operate, equipment is simple, low in cost, photocatalysis efficiency is high, the good, cleanliness without any pollution of bactericidal effect etc. is excellent
Point may be widely used for killing the bacterium (such as E. coli bacteria, golden staphylococci) in water body, have very high application
Value and commercial value.
(3) in the method for the present invention, modified carbon quantum dot used loads hollow tubular carbon nitride photocatalyst, with hollow tubular
Carbonitride is carrier, and load has modified carbon quantum dot on hollow tubular carbonitride.In the present invention, hollow tubular carbonitride have than
The advantages that surface area is big, pore quantity is more, photo-generated carrier separates and migration rate is fast, absorbing ability is strong, photocatalytic activity is high,
It is the novel carriers that a kind of appearance structure is novel, photocatalysis performance is excellent.On this basis, since modified carbon quantum dot is with upper
The features such as transfer capability is strong, toxicity is low and good biocompatibility is supported on hollow tubular carbonitride by that will be modified carbon quantum dot
When upper, modified carbon quantum dot as electronics conductively, the light induced electron that carbonitride can be enable to generate under light illumination and hole
Faster separation, while also can be improved the absorption spectrum of carbonitride, broader absorption spectrum is obtained, thus more effectively benefit
With visible light, better photocatalytic activity is obtained.As it can be seen that the modified carbon quantum dot of the present invention loads the photocatalysis of hollow tubular carbonitride
Agent have large specific surface area, pore quantity is more, active site is more, photo-generated carrier separates and migration rate is fast, absorbing ability by force,
The advantages that photocatalytic activity is high, while also there is high stability and strong photocatalysis efficiency, it can be widely applied in processing environment
Organic pollutant can be used for killing the harmful bacteria in environment, there is good application value and application prospect.
(4) in the method for the present invention, the preparation method of modified carbon quantum dot load hollow tubular carbon nitride photocatalyst used,
It, will be during modified carbon quantum dot be supported on by mixing and drying using hollow tubular carbonitride and carbon modified quantum dot solution as raw material
On blank pipe shape carbonitride, it can be prepared that large specific surface area, pore quantity be more, the modification carbon quantum dot load more than active site
Hollow tubular carbon nitride photocatalyst.The preparation method of the modified carbon quantum dot load hollow tubular carbon nitride photocatalyst of the present invention
It is convenient, easy to operate, without secondary pollution to environment with synthesizing, meet needs of production, is suitable for large scale preparation, is convenient for
Industrialized utilization.
(5) in the method for the present invention, hollow tubular carbonitride is to pass through hydro-thermal and high temperature using urea and melamine as raw material
Hollow tubular carbonitride is prepared in calcining, wherein azotized carbon nano pipe presoma (cyanuric acid) is formed by hydro-thermal reaction,
Then it is calcined under the high temperature conditions, melamine and cyanuric acid are self-assembly of hollow tubular carbonitride photocatalysis at this time
Agent, and urea can generate ammonia and carbon dioxide at high temperature in preparation process, and hollow tubular carbonitride tube wall is made to form hole.
In the present invention, hollow tubular carbonitride is prepared using template-free method for the first time, and thus obtained hollow tubular carbonitride is enhancing
It can reduce photochemical catalyst semiconductor band gap width while photocatalyst surface area and hole size, to improve photocatalysis
Efficiency, this is the novel carriers that a kind of appearance structure is novel, photocatalysis performance is excellent.In addition, the template-free method that the present invention uses
In, without environmentally harmful raw material, preparation process is simple and convenient, largely can quickly prepare.Hollow tubular nitrogen of the present invention
Change carbon photochemical catalyst preparation method have simple process, raw material sources are wide, low in cost, preparation efficiency is high, yield is high and right
The advantages that environment is without secondary pollution.
Detailed description of the invention
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, the technical scheme in the embodiment of the invention is clearly and completely described.
Fig. 1 is modified carbon quantum dot load hollow tubular carbon nitride photocatalyst obtained in the embodiment of the present invention 1
(HTCN-C2) scanning electron microscope diagram.
Fig. 2 is modified carbon quantum dot load hollow tubular carbon nitride photocatalyst obtained in the embodiment of the present invention 1
(HTCN-C2) transmission electron microscope(TEM) figure.
Fig. 3 is modified carbon quantum dot load hollow tubular carbon nitride photocatalyst obtained in the embodiment of the present invention 1
The X-ray diffraction of (HTCN-C0.5, HTCN-C1, HTCN-C2, HTCN-C3) compares map.
Fig. 4 is modified carbon quantum dot load hollow tubular carbon nitride photocatalyst obtained in the embodiment of the present invention 1
The UV-vis DRS figure of (HTCN-C0.5, HTCN-C1, HTCN-C2, HTCN-C3).
Fig. 5 is that different modified carbon quantum dots load hollow tubular carbon nitride photocatalyst to Fourth Ring in the embodiment of the present invention 1
The photocatalytic degradation figure of element.
Fig. 6 is that modified carbon quantum dot loads hollow tubular carbon nitride photocatalyst (HTCN-C2) in the embodiment of the present invention 1
The circulation figure of recycling degradation tetracycline.
Fig. 7 is that modified carbon quantum dot loads hollow tubular carbon nitride photocatalyst (HTCN-C2) instead in the embodiment of the present invention 1
Answer the X ray diffracting spectrum of front and back.
Fig. 8 is that modified carbon quantum dot load hollow tubular carbon nitride photocatalyst (HTCN-C2) is right in the embodiment of the present invention 2
The photocatalytic degradation figure of Escherichia coli.
Specific embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
It limits the scope of the invention.
In following present invention embodiment, unless otherwise noted, used material and instrument are commercially available, used technique
For common process, used equipment is conventional equipment, and the data obtained is the average value for repeating experiment more than three times.
Embodiment 1:
A method of organic pollutant, tool are handled using modified carbon quantum dot load hollow tubular carbon nitride photocatalyst
Body is to load hollow tubular carbon nitride photocatalyst using modified carbon quantum dot to handle tetracycline wastewater, comprising the following steps:
Weigh modified carbon quantum dot load hollow tubular carbon nitride photocatalyst (HTCN-C0.5, HTCN-C1, HTCN-C2,
HTCN-C3), each 30mg is respectively added to 30mL, in the tetracycline wastewater that concentration is 20mg/L, in the dark, revolving speed 400r/
Magnetic agitation 1h under conditions of min opens light source (300W xenon lamp) after reaching adsorption equilibrium, irradiates and carry out under simulated solar irradiation
Light-catalyzed reaction 1h completes the degradation to tetracycline.
In the present embodiment, modified carbon quantum dot load hollow tubular carbon nitride photocatalyst (HTCN-C0.5) used, in
Blank pipe shape carbonitride is carrier, and load has modified carbon quantum dot on hollow tubular carbonitride.Hollow tubular carbonitride is with urea
It is prepared for raw material by hydro-thermal and calcining with melamine, wherein the molar ratio of urea and melamine is 3: 1.
In the present embodiment, the system of modified carbon quantum dot load hollow tubular carbon nitride photocatalyst (HTCN-C0.5) used
Preparation Method, comprising the following steps:
0.2g hollow tubular carbonitride is suspended in 30mL ultrapure water, 0.5mL carbon modified quantum dot solution, mixing is added
Uniformly, it is dried at 80 DEG C, obtains modified carbon quantum dot load hollow tubular carbon nitride photocatalyst, number HTCN-C0.5.
In the present embodiment, hollow tubular carbonitride used passes through hydro-thermal and calcining using urea and melamine as raw material
Be prepared, wherein the molar ratio of urea and melamine be 3: 1, preparation method specifically includes the following steps:
S1, urea and melamine ground respectively, take 9.56g urea and 6g melamine be dissolved in 70mL go from
In sub- water, ultrasonic 1h stirs 8h, is uniformly mixed, obtains mixed solution.
S2, mixed solution obtained in step S1 is transferred in 100mL autoclave, hydro-thermal reaction is carried out at 180 DEG C
24 hours, after natural cooling, gained reaction product was respectively cleaned 3 times using water and ethyl alcohol, and filtering (specially filters), at 70 DEG C
Dry 12h, obtains presoma.
S3, presoma obtained in step S2 is put into crucible, is placed in Muffle furnace, with 2.3 DEG C/min of heating speed
Rate is heated to 550 DEG C and is calcined, and keeps the temperature 240min at 550 DEG C, be drawn off and grind after natural cooling, obtains
Blank pipe shape carbonitride, number HTCN.
In the present embodiment, the preparation method of modified quantum dot solution used, comprising the following steps:
(1) it takes 5mmol sodium citrate and 5mmol cysteine to mix in ultrapure water, is stirred in the case where revolving speed is 400r/min
1h is mixed, is uniformly mixed, obtains precursor solution.
(2) precursor solution obtained in step (1) is transferred in 100mL hydrothermal reaction kettle, keeps the temperature 6 in 200 DEG C
Hour, after natural cooling, dialysis 12h is carried out using product of the bag filter to hydro-thermal reaction, obtains modified quantum dot solution, compiled
Number be CQD.
In the present embodiment, the preparation of modified carbon quantum dot load hollow tubular carbon nitride photocatalyst (HTCN-C1) used
The preparation method of method, modified carbon quantum dot load hollow tubular carbon nitride photocatalyst (HTCN-C0.5) is essentially identical, difference
Be only that: the volume of carbon modified quantum dot solution is 1mL.
In the present embodiment, the preparation of modified carbon quantum dot load hollow tubular carbon nitride photocatalyst (HTCN-C2) used
The preparation method of method, modified carbon quantum dot load hollow tubular carbon nitride photocatalyst (HTCN-C0.5) is essentially identical, difference
Be only that: the volume of carbon modified quantum dot solution is 2mL.
In the present embodiment, the preparation of modified carbon quantum dot load hollow tubular carbon nitride photocatalyst (HTCN-C3) used
The preparation method of method, modified carbon quantum dot load hollow tubular carbon nitride photocatalyst (HTCN-C0.5) is essentially identical, difference
Be only that: the volume of carbon modified quantum dot solution is 3mL.
Fig. 1 is modified carbon quantum dot load hollow tubular carbon nitride photocatalyst obtained in the embodiment of the present invention 1
(HTCN-C2) scanning electron microscope diagram.Fig. 2 is modified carbon quantum dot load hollow tube obtained in the embodiment of the present invention 1
The transmission electron microscope(TEM) figure of shape carbon nitride photocatalyst (HTCN-C2).It can be seen that the modified carbon amounts of the present invention from Fig. 1 and Fig. 2
Apparent hollow tubular structure is presented in son point load hollow tubular carbonitride, and there is part nano aperture on its surface；Meanwhile
From figure 2 it can be seen that modified carbon quantum dot is supported on hollow tubular carbonitride.
Fig. 3 is modified carbon quantum dot load hollow tubular carbon nitride photocatalyst obtained in the embodiment of the present invention 1
The X-ray diffraction of (HTCN-C0.5, HTCN-C1, HTCN-C2, HTCN-C3) compares map.As shown in figure 3, all samples peak type
It is sharp and prominent, illustrate that the crystallinity of sample is preferable, wherein occur two at 13.1 ° and 27.2 ° and significantly belong to graphite
The XRD diffraction maximum of phase carbon nitride (100) and (002) crystal face, it was demonstrated that the product of preparation is g-C3N4；Meanwhile using different volumes
The X ray diffracting spectrum of the load hollow tubular carbon nitride photocatalyst of modification carbon quantum dot obtained by carbon modified quantum dot solution
Similar, no other miscellaneous peaks occur, and illustrate that the load of modified carbon quantum dot does not cause g-C3N4Topological structure change.
Fig. 4 is modified carbon quantum dot load hollow tubular carbon nitride photocatalyst obtained in the embodiment of the present invention 1
The UV-vis DRS figure of (HTCN-C0.5, HTCN-C1, HTCN-C2, HTCN-C3).As shown in figure 4, using different volumes
Carbon modified quantum dot solution obtained by modification carbon quantum dot load hollow tubular carbon nitride photocatalyst extinction wavelength it is equal
In 500nm or so, compared to the extinction wavelength (470nm or so) of monomer carbonitride, light abstraction width improves,
Improve the utilization rate of light.
During the magnetic agitation of the present embodiment, 2mL sample is taken every 15min, and sample is centrifuged.Take centrifugation institute
It obtains supernatant and absorbance is measured by ultraviolet-uisible spectrophotometer, the concentration of tetracycline is determined, to obtain different modifications
Carbon quantum dot loads hollow tubular carbon nitride photocatalyst to the photocatalysis effect of tetracycline.
Fig. 5 is that different modified carbon quantum dots load hollow tubular carbon nitride photocatalyst to Fourth Ring in the embodiment of the present invention 1
The photocatalytic degradation figure of element.As shown in Figure 5, the modified carbon quantum dot load hollow tubular carbon nitride photocatalyst of the present invention can have
Tetracycline in effect removal waste water, has preferable removal effect, wherein modified carbon quantum dot loads hollow tubular carbonitride light
The removal rate of catalyst (HTCN-C2) can achieve 82.67%, and the total removal rate of monomer carbonitride and hollow tubular carbonitride
Only 30.16% and 51.85%, for this explanation by loaded modified carbon quantum dot, the photocatalysis performance of hollow tubular carbonitride is equal
It greatly promotes, thus suitable modified carbon quantum dot load capacity is selected to load hollow tubular carbonitride to modified carbon quantum dot is improved
The photocatalysis performance of photochemical catalyst has great significance.
Fig. 6 is that modified carbon quantum dot loads hollow tubular carbon nitride photocatalyst (HTCN-C2) in the embodiment of the present invention 1
The circulation figure of recycling degradation tetracycline.It will be appreciated from fig. 6 that modified carbon quantum dot loads hollow tubular carbon nitride photocatalyst
(HTCN-C2) sufficiently stable, degradation removal rate still has 79.87% after circulation four times, only 2.8% loss, it is seen that modified
Carbon quantum dot loads the photocatalysis stability of hollow tubular carbon nitride photocatalyst (HTCN-C2).
Hollow tubular carbon nitride photocatalyst is loaded to the modification carbon quantum dot before and after processing tetracycline in embodiment 1
(HTCN-C2) X-ray diffraction analysis is carried out, as a result as shown in Figure 7.Fig. 7 is modified carbon quantum dot load in the embodiment of the present invention 1
The X ray diffracting spectrum of hollow tubular carbon nitride photocatalyst (HTCN-C2) reaction front and back.As shown in fig. 7, carbon modified of the present invention
The X ray diffracting spectrum of quantum dot load hollow tubular carbon nitride photocatalyst reaction front and back remains unchanged and peak type is sharp, this
Illustrate that reaction front-end geometry remains unchanged and crystallinity is good, there is preferable stability.
Embodiment 3:
A method of hollow tubular carbon nitride photocatalyst photo-catalyst being loaded using modified carbon quantum dot, specially
Escherichia coli are handled using modified carbon quantum dot load hollow tubular carbon nitride photocatalyst, comprising the following steps:
Weigh modified carbon quantum dot load hollow tubular carbon nitride photocatalyst (HTCN- obtained in 30mg embodiment 1
C2), it is added in the sterile water of 49.5mL, it is 3 × 10 that 0.5mL, concentration 30mL, concentration, which is added,9The Escherichia coli of CFU/mL
Solution, the concentration dilution of Escherichia coli is 3 × 10 in system at this time7CFU/mL is opened light source (300W xenon lamp), in simulated solar
Irradiation carries out photo-catalyst reaction 1h under light, completes the inactivation to Escherichia coli.
Every reaction liquid for taking 100uL for 15 minutes, then these bacterium solutions of dilution appropriate, are finally counted with colony counting method
E. coli clones are calculated, the inactivation of modified carbon quantum dot load hollow tubular carbon nitride photocatalyst (HTCN-C2) is finally obtained
Performance.
Fig. 8 is that modified carbon quantum dot load hollow tubular carbon nitride photocatalyst (HTCN-C2) is right in the embodiment of the present invention 2
The photocatalytic degradation figure of Escherichia coli.As shown in Figure 8, after illumination 1 hour, modified carbon quantum dot loads hollow tubular carbonitride light
Catalyst (HTCN-C2) shows excellent bactericidal property.
In conclusion the present invention handles organic contamination using modified carbon quantum dot load hollow tubular carbon nitride photocatalyst
The method of object and photo-catalyst, by utilizing with unique appearance structure, big specific surface area and hole configurations, quickly
Photo-generated carrier separates, the modification carbon quantum dot of transfer ability loads hollow tubular carbon nitride photocatalyst, can high efficiency photocatalysis
The bacterium in organic pollutant (such as antibiotic) and removal water body environment in degrading waste water, has wide in photocatalysis field
Prospect.
Above embodiments are only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned reality
Apply example.All technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It is noted that being led for this technology
For the those of ordinary skill in domain, improvements and modifications without departing from the principle of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of method using modified carbon quantum dot load hollow tubular carbon nitride photocatalyst processing organic pollutant, special
Sign is, comprising the following steps: by modified carbon quantum dot load hollow tubular carbon nitride photocatalyst and organic pollutant wastewater
Mixing carries out photocatalytic degradation reaction after reaching adsorption equilibrium, completes the processing to organic pollutant；The modified carbon quantum dot
Loading hollow tubular carbon nitride photocatalyst is using hollow tubular carbonitride as carrier, and loading on the hollow tubular carbonitride has
Modified carbon quantum dot；The hollow tubular carbonitride is to be prepared into using urea and melamine as raw material by hydro-thermal and calcining
It arrives；The molar ratio of the urea and melamine is 1~5: 1.
2. the method according to claim 1, wherein the modified carbon quantum dot loads hollow tubular carbonitride light
Catalyst and organic pollutant wastewater ratio are 20mg~30mg: 30mL；The organic pollutant wastewater is antibiotic waste water；Institute
Stating the antibiotic in antibiotic waste water is tetracycline and/or sulfamethazine etc.；Antibiotic in the antibiotic waste water
Concentration≤20mg/L；Described be mixed into is stirred under dark condition；The revolving speed of the stirring is 400r/min；The stirring
Time be 60min；The photocatalytic degradation reaction carries out under illumination condition；The light source of the illumination condition is the xenon of 300W
Lamp；The time of the photocatalytic degradation reaction is 1h~2h.
3. a kind of method using modified carbon quantum dot load hollow tubular carbon nitride photocatalyst photo-catalyst, feature exist
In, comprising the following steps: modified carbon quantum dot load hollow tubular carbon nitride photocatalyst is mixed with bacterial solution and carries out light
Catalytically bactericidal process reaction, completes the inactivation to bacterium；The modified carbon quantum dot load hollow tubular carbon nitride photocatalyst be with
Hollow tubular carbonitride is carrier, and load has modified carbon quantum dot on the hollow tubular carbonitride；The hollow tubular nitridation
Carbon is to be prepared using urea and melamine as raw material by hydro-thermal and calcining；The molar ratio of the urea and melamine is
1~5: 1.
4. according to the method described in claim 3, it is characterized in that, the modified carbon quantum dot loads hollow tubular carbonitride light
Catalyst and bacterial solution ratio are 20mg~30mg: 0.5mL；Bacterium in the bacterial solution is Escherichia coli and/or gold
Staphylococcus；Concentration≤3 × 10 of bacterium in the bacterial solution9CFU/mL；The photo-catalyst reaction is in illumination condition
Lower progress；The light source of the illumination condition is the xenon lamp of 300w；The time of the photo-catalyst reaction is 1h~2h.
5. method according to any one of claims 1 to 4, which is characterized in that the modified carbon quantum dot load is hollow
The following steps are included: hollow tubular carbonitride is suspended in water, addition is modified the preparation method of tubulose carbon nitride photocatalyst
Carbon quantum dot solution, drying obtain modified carbon quantum dot load hollow tubular carbon nitride photocatalyst.
6. according to the method described in claim 5, it is characterized in that, the preparation method of the hollow tubular carbonitride includes following
Step:
S1, urea and melamine are dissolved in solvent, ultrasound, stirring obtains mixed solution；
S2, mixed solution obtained in step S1 is subjected to hydro-thermal reaction, cleaned, filtered, it is dry, obtain presoma；
S3, presoma obtained in step S2 is calcined, grinds, obtains hollow tubular carbonitride.
7. according to the method described in claim 6, it is characterized in that, in the step S1, the urea and melamine rub
You are than being 1~5: 1；The solvent is water；The time of the ultrasound is 0.5h~3h, and the time of the stirring is 8h~18h；
In the step S2, temperature >=180 DEG C of the hydro-thermal reaction；The time of the hydro-thermal reaction is for 24 hours~36h；It is described
Dry temperature is 60 DEG C~85 DEG C；The time of the drying is 8h~12h；
In the step S3, heating rate is 2.3 DEG C/min~5 DEG C/min in the calcination process；The temperature of the calcining is
550 DEG C~650 DEG C；The time of the calcining is 4h~6h.
8. according to the method described in claim 5, it is characterized in that, the preparation method of the carbon modified quantum dot solution include with
Lower step:
(1) sodium citrate and cysteine are dissolved in solvent, stir, obtains precursor solution；
(2) precursor solution obtained in step (1) is subjected to hydro-thermal reaction, dialysis obtains carbon modified quantum dot solution.
9. according to the method described in claim 8, it is characterized in that, in the step (1), the sodium citrate and cysteine
Molar ratio be 1: 1；The solvent is water；The revolving speed of the stirring is 300r/min~500r/min；The time of the stirring
For 1h~2h；
In the step (2), the temperature of the hydro-thermal reaction is 180 DEG C~220 DEG C；The time of the hydro-thermal reaction be 6h~
8h；The time of the dialysis is 12h~for 24 hours.
10. according to the method described in claim 5, it is characterized in that, the ratio of the hollow tubular carbonitride and water is 0.2g:
30mL~50mL；The ratio of the hollow tubular carbonitride and carbon modified quantum dot solution is 0.2g: 0.5mL~3mL；It is described to change
Property carbon quantum dot solution concentration be 1mg/mL；The temperature of the drying is 70 DEG C~80 DEG C；The time of the drying be 18h~
24h。
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