CN107803215A - A kind of carbon point molybdenum trioxide is with nitrogenizing carbon composite photocatalyst and its preparation method and application - Google Patents
A kind of carbon point molybdenum trioxide is with nitrogenizing carbon composite photocatalyst and its preparation method and application Download PDFInfo
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 title claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 56
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000012546 transfer Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 239000004098 Tetracycline Substances 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 9
- 229960002180 tetracycline Drugs 0.000 claims description 9
- 229930101283 tetracycline Natural products 0.000 claims description 9
- 235000019364 tetracycline Nutrition 0.000 claims description 9
- 150000003522 tetracyclines Chemical class 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 7
- 238000006471 dimerization reaction Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000003801 milling Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 230000003115 biocidal effect Effects 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 150000004685 tetrahydrates Chemical class 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- 239000003643 water by type Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000003242 anti bacterial agent Substances 0.000 claims description 2
- 229940088710 antibiotic agent Drugs 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 150000004767 nitrides Chemical class 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000011017 operating method Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 235000015165 citric acid Nutrition 0.000 description 5
- 238000006303 photolysis reaction Methods 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 206010003497 Asphyxia Diseases 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000001055 reflectance spectroscopy Methods 0.000 description 2
- 239000012984 antibiotic solution Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002023 wood Substances 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
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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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
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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
- B01J37/082—Decomposition and pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
- 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
- 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
- C02F2101/38—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
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Abstract
The invention belongs to photocatalysis field, discloses the preparation method and application that a kind of carbon point molybdenum trioxide is total to composite nitride C catalyst.Including following operating procedure：S1. MoO is prepared3Powder；S2. CDs powder is prepared；S3. C is prepared3N4Powder；S4. MoO is prepared3‑CDs/C3N4Composite catalyst：Weigh C3N4Powder, MoO3Powder and the mixing of CDs powder, absolute ethyl alcohol is added, after ultrasonic disperse, the temperature of mixed solution is risen to 75 DEG C and stirring is evaporated, it is subsequently moved in baking oven dry with 100 DEG C of temperature, powder solid is taken out after cooling, and grinding is uniform, transfers them in Muffle furnace and is reacted, after it is cooled to room temperature, mill, sieve, obtain carbon point molybdenum trioxide and nitridation carbon composite photocatalyst.Preparation method repeatability and controllability of the present invention are good, and stability of material is good, can meet volume production requirement well, there is higher application prospect and use value.
Description
Technical field
The invention belongs to photocatalysis field, is related to a kind of composite photo-catalyst and its preparation method and application, and in particular to
A kind of carbon point-molybdenum trioxide is with nitrogenizing carbon composite photocatalyst and its preparation method and application.
Background technology
In recent years, because the Tough questions of energy shortage, Photocatalitic Technique of Semiconductor increasingly cause researcher
Concern.Carbonitride (the g-C of graphite-phase3N4) it is a kind of novel metalloid semi-conducting material for possessing visible light-responded ability, can band
Gap width is medium (2.7eV), has the advantages of low production cost and simple preparation method.In addition, g-C3N4Also there is chemistry
, toxicity low the features such as high with heat endurance.However, because its light utilization efficiency is low, the defects of light induced electron and high hole-recombination rate,
Limit g-C3N4In the practical application of photocatalysis field.
Molybdenum trioxide (MoO3) it is that a kind of can absorb the stable semi-conducting material of visible ray and physicochemical properties, forbidden band
About 2.8eV.The characteristics of using molybdenum trioxide band gap locations, introduce g-C3N4The hetero-junctions that recombination energy is formed therewith, and contribute to
Improve g-C3N4The photocatalysis efficiency of material.
Carbon point (carbon dots, CDs) is using Elements C as main component, with reference to one kind of the elements such as H, O, N composition
The material of similar semiconductor-quantum-point, grain diameter is from several nanometers to tens nanometer.In photocatalysis field, research finds carbon
Point has upper converting photoluminescent performance, and the light at 550-800nm can be converted to 325-425nm light.In addition, carbon point also has
Standby superior electronics transfer and storage capacity, thus there is great application potential in photocatalysis field, and therefore receive wide
General concern.
The content of the invention
In order to overcome shortcoming and defect present in prior art, primary and foremost purpose of the invention be to provide a kind of carbon point-
Molybdenum trioxide and carbonitride (MoO3-CDs/C3N4) composite photo-catalyst preparation method；
The MoO prepared another object of the present invention is to provide a kind of above-mentioned preparation method3-CDs/C3N4Composite photocatalyst
Agent.Catalysis material prepared by this method has high visible response and the high-performance of low photo-generated carrier combined efficiency, and
Can tetracycline in efficient degradation water under radiation of visible light.
It is still another object of the present invention to provide a kind of above-mentioned MoO3-CDs/C3N4The application of composite photo-catalyst.
The purpose of the present invention is realized by following technical proposals：
The preparation method of a kind of carbon point-molybdenum trioxide and nitridation carbon composite photocatalyst, including following operating procedure：
S1. MoO is prepared3Powder：Seven Ammonium paramolybdate tetrahydrates are weighed to be placed in alumina crucible, it is anti-in 60-90 DEG C of temperature heating
Should after be transferred in Muffle furnace, and be warming up to 400-550 DEG C and keep the temperature to be calcined；After it is cooled to room temperature, grind
Honed sieve, obtains MoO3Powder；
S2. CDs powder is prepared：Urea and citric acid are weighed respectively, ultra-pure water are added, by it by being moved to after ultrasonic dissolution
Hydro-thermal reaction is carried out in polytetrafluoroethylene (PTFE) high temperature hydrothermal reaction kettle；Treat that it is cooled to room temperature, obtain the aqueous solution, by solution centrifugal
Bulky grain is removed, drying obtains CDs powder after milling；
S3. C is prepared3N4Powder：Weigh cyanamid dimerization to be placed in crucible, and put into Muffle furnace with 2-3 DEG C/min heating speed
Rate rises to 500-600 DEG C and keeps the temperature to be reacted；Taken out after it is cooled to room temperature, grinding sieving obtains C3N4Powder；
S4. MoO is prepared3-CDs/C3N4Composite catalyst：Weigh C3N4Powder, MoO3Powder and the mixing of CDs powder, are added
Absolute ethyl alcohol, after ultrasonic disperse, the temperature of mixed solution is risen to 75 DEG C and stirring is evaporated, is subsequently moved in baking oven with 100
DEG C temperature is dried, and takes out powder solid after cooling, grinding is uniform, transfers them in Muffle furnace and is reacted, treats its cooling
To room temperature, mill, sieve, obtain carbon point-molybdenum trioxide and nitridation carbon composite photocatalyst (MoO3-CDs/C3N4Composite catalyzing
Agent).
Heating rate described in step S1 is 2-4 DEG C/min, and the time of the heating response is 10~12h；The calcining
Time be 4~6h；The milling time is 30min..
The mass ratio of urea and citric acid described in step S2 is (0.28~0.50)：1；The temperature of the hydro-thermal reaction is
160-185 DEG C, reaction time 3-5h.
The time reacted described in step S3 is 2-4h.
C described in step S43N4Powder, MoO3The mass ratio of powder and CDs powder is 0.9-1.0：0.03-0.05：
0.0015-0.003；The time of the ultrasonic disperse is 2-3h；The time of the oven drying is 10-12h；In the Muffle furnace
Heating rate is 2-3 DEG C/min, and final temperature is 250-350 DEG C, and the time reacted in Muffle furnace is 4-8h.
Seven Ammonium paramolybdate tetrahydrates described in step S1 are 3-5g；Urea and citric acid are respectively 1.0-1.5g described in step S2
And 3.0-3.5g, for the addition of the ultra-pure water on the basis of urea, 1g urea adds 10ml ultra-pure waters；Dimerization described in step S3
Cyanamide is 3-5g；C described in step S43N4Powder, MoO3Powder and CDs powder be respectively 0.9-1.0g, 0.03-0.05g and
0.0015-0.003g。
A kind of carbon point-molybdenum trioxide being prepared by above-mentioned preparation method and nitridation carbon composite photocatalyst.
Application of the above-mentioned carbon point-molybdenum trioxide with nitridation carbon composite photocatalyst in field of antibiotics of degrading.It is described
Antibiotic is tetracycline.
Above-mentioned carbon point-molybdenum trioxide and carbonitride (MoO3-CDs/C3N4) composite photo-catalyst degrades under simulated solar irradiation
Application in antibiotic, method are as follows：0.03g composite photo-catalysts are weighed in quartzy photodissociation pipe, using volume as 50mL concentration
Antibiotic solution for 20mg/L is target contaminant, and it is light source to configure 420nm optical filters by using 350w xenon lamps, by photodissociation
Pipe, which is placed under light source, irradiates 60-120min, uses the concentration of remaining antibiotic in high-efficient liquid phase color spectrometry solution.
The present invention is had the following advantages relative to prior art and effect：
(1) in photochemical catalyst of the present invention, MoO is introduced3As composite object, can suppress to be catalyzed by forming hetero-junctions
Electronics and hole is compound in journey, so as to improve photocatalysis efficiency.
(2) present invention introduces carbon point in composite photo-catalyst, can be by low energy using the upper conversion light function of carbon point
Light is converted to the light of high-energy and is utilized；In addition, carbon point also has of short duration stored electrons ability, and can also reach makes
The effect of photo-generated carrier separation, so as to improve photocatalysis efficiency.
(3) preparation method repeatability and controllability of the present invention are good, and stability of material is good, can meet that volume production will well
Ask, there is higher application prospect and use value.
Brief description of the drawings
Fig. 1 is the MoO in embodiment 13-CDs/C3N4TEM collection of illustrative plates.
Fig. 2 is the MoO in embodiment 13-CDs/C3N4With the MoO in comparative example 13/C3N4UV Diffuse Reflectance Spectroscopy spectrum
Figure.
Fig. 3 is the MoO in embodiment 13-CDs/C3N4, C3N4With the MoO in comparative example 13/C3N4Fluorescence pattern.
Fig. 4 is the MoO in embodiment 13-CDs/C3N4, C3N4With the MoO in comparative example 13/C3N4Tetracycline is removed respectively
Efficiency chart.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
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
The preparation of a kind of carbon point and molybdenum trioxide composite nitride carbon photochemical catalyst, comprises the following steps：
(1) the seven water ammonium molybdates for weighing 3g are placed in alumina crucible, and Muffle furnace is transferred to after heating 12h with 80 DEG C of temperature
In, rise to 450 DEG C with 2.5 DEG C/min heating rates and keep the temperature to carry out reaction 5h；After it is cooled to room temperature, grinding
30min, sieving, obtains canescence MoO3Powder；
(2) 1g urea and 3g citric acids are weighed respectively in 50ml beakers, add 10ml ultra-pure waters, ultrasonic dissolution 10min
After move in polytetrafluoroethylene (PTFE) high temperature hydrothermal reaction kettle, with 180 DEG C of thermotonus 5h；Treat that it is cooled to room temperature, obtain brown
The aqueous solution, solution centrifugal is removed into bulky grain, drying obtains brownish black CDs powder after milling；
(3) 3g cyanamid dimerizations are weighed to be placed in alumina crucible, are put it into Muffle furnace with 2.8 DEG C/min heating rates
Rise to 550 DEG C and keep the temperature to carry out reaction 3h；Taken out after it is cooled to room temperature, grinding sieving obtains faint yellow C3N4Powder
End.
(4) C obtained by step (3) is weighed respectively3N4MoO obtained by powder 0.965g, step (1)3Powder 0.03g and step
(2) gained CDs powder 0.005g, add 50mL absolute ethyl alcohol, and its temperature is risen into 75 DEG C of stirrings after ultrasonic disperse 2h is evaporated,
It is subsequently moved in baking oven with 100 DEG C of dry 12h, takes out powder solid after cooling, grinds 30min, transfer them to Muffle furnace
In rise to 300 DEG C with 2.5 DEG C/min heating rates and keep the temperature to carry out reaction 5h；After it is cooled to room temperature, mill, mistake
Sieve, obtains MoO3-CDs/C3N4Composite catalyst.
Comparative example 1
A kind of preparation of molybdenum trioxide doping sheet carbon nitride photocatalyst, comprises the following steps：
1. the seven water ammonium molybdates for weighing 4.5g are placed in alumina crucible, Muffle is moved it to after drying 11h with 80 DEG C of temperature
In stove, rise to 400 DEG C with 2 DEG C/min heating rates and keep the temperature to carry out reaction 4h；After it is cooled to room temperature, grinding
30min, sieving, obtains pale asphyxia MoO3Powder；
2. weighing 4.2g cyanamid dimerizations to be placed in alumina crucible, put it into Muffle furnace with 2.0 DEG C/min heating speed
Rate rises to 600 DEG C and keeps the temperature to carry out reaction 2h；Taken out after it is cooled to room temperature, grinding sieving obtains faint yellow C3N4
Powder.
3 weigh 1.000g carbonitrides and 0.04g MoO respectively3Powder, add 50mL absolute ethyl alcohol, ultrasonic disperse 3h
Its temperature is risen into 75 DEG C of stirrings afterwards to be evaporated, is subsequently moved in baking oven, with 100 DEG C of dry 11h, take out powder solid after cooling,
40min is ground, is transferred them to and is risen to 250 DEG C with 2 DEG C/min heating rates in Muffle furnace and keep the temperature to carry out reaction 8h；
After it is cooled to room temperature, mill, sieve, obtain MoO3/C3N4Composite catalyst.
The MoO that will be prepared in embodiment 13-CDs/C3N4Tem analysis is carried out, as a result as shown in Figure 1.Understand as shown in Figure 1,
CDs is good to be dispersed in photochemical catalyst, the MoO of polygon grains3It is also attached to sheet C3N4Surface, show the composite wood
Expect successfully to prepare.
By the MoO in embodiment 13-CDs/C3N4, comparative example 1 MoO3/C3N4Carry out UV Diffuse Reflectance Spectroscopy analysis, knot
Fruit is as shown in Figure 2.By Tu Ke get, adulterate the photoreactivation catalyst after CDs has obvious enhancing at visible light-responded aspect, this table
It is bright it is compound after material property enhancing.
By the C in embodiment 13N4、MoO3-CDs/C3N4, MoO in comparative example 13/C3N4Fluorescence analysis is carried out respectively, is tied
Fruit is as shown in Figure 3.By scheming, MoO is adulterated3Fluorescence intensity significantly decreases afterwards, and this is likely to be MoO3With C3N4It is caused different
Matter knot reduces the compound of photo-generated carrier, and fluorescence decline becomes apparent from after composite carbon point, because carbon point stored electrons
The low recombination rate for the carrier that ability is caused, so as to improve the photocatalytic activity of material.
Embodiment 2
The preparation of a kind of carbon point and molybdenum trioxide composite nitride carbon photochemical catalyst, comprises the following steps：
(1) the seven water ammonium molybdates for weighing 5g are placed in alumina crucible, and Muffle furnace is moved it to after drying 10h with 90 DEG C of temperature
In, rise to 550 DEG C with 4 DEG C/min heating rates and keep the temperature to carry out reaction 6h；After it is cooled to room temperature, grinding
30min, sieving, obtains pale asphyxia MoO3Powder；
(2) 1.5g urea and 3.3g citric acids are weighed respectively in 50mL beakers, add 15mL ultra-pure waters, ultrasonic dissolution
Moved to after 10min in polytetrafluoroethylene (PTFE) high temperature hydrothermal reaction kettle, with 160 DEG C of thermotonus 3.5h；Treat that it is cooled to room temperature, obtain
To brown aqueous solution, solution centrifugal is removed into bulky grain, drying obtains brownish black CDs powder after milling；
(3) 5g cyanamid dimerizations are weighed to be placed in alumina crucible, are put it into Muffle furnace with 3 DEG C/min heating rate liters
To 500 DEG C and the temperature is kept to carry out reaction 4h.Taken out after it is cooled to room temperature, grinding sieving obtains faint yellow C3N4Solid；
(4) C obtained by step (3) is weighed respectively3N4MoO obtained by powder 0.90g, step (1)3Powder 0.05g and step
(2) gained CDs powder 0.003g, add 50mL absolute ethyl alcohol, and its temperature is risen into 75 DEG C of stirrings after ultrasonic disperse 2h is evaporated,
It is subsequently moved in baking oven with 100 DEG C of dry 10h, takes out powder solid after cooling, grinds 30min, transfer them to Muffle furnace
In rise to 350 DEG C with 3 DEG C/min heating rates and keep the temperature to carry out reaction 4h；After it is cooled to room temperature, mill, mistake
Sieve, obtains MoO3-CDs/C3N4Composite catalyst.
Embodiment 3
A kind of application of carbon point of the invention and molybdenum trioxide composite nitride carbon photocatalyst for degrading antibiotic, including it is following
Step：
(1) weigh 30mg and implement photochemical catalyst MoO made from 13-CDs/C3N4It is placed in quartzy photodissociation pipe, adding concentration is
20mg/L volumes are 50mL tetracycline, and stirring and adsorbing 30min in photodissociation instrument is placed in after ultrasonic disperse 5min.
(2) light source carries out light-catalyzed reaction using 350W xenon lamps configuration 420nm optical filters, reaction time 90min, treats anti-
Remaining tetracycline concentration (C in liquid chromatographic detection solution is used after having answeredt).According to according to formula P=(C0-Ct) * 100% count
Calculate the clearance of tetracycline, wherein C0For the initial concentration of tetracycline.As a result it is as shown in Figure 4.
(3) obtained C in 30mg embodiments 1 is weighed3N4, repeat step (1), (2), calculate the removal of corresponding tetracycline
Rate, as a result as shown in Figure 4.
(4) obtained MoO in 30mg embodiments 1 is weighed3/C3N4, repeat step (1), (2), calculate corresponding tetracycline
Clearance, as a result as shown in Figure 4.
It can obtain by Fig. 4, the photoreactivation catalyst MoO prepared in embodiment 13-CDs/C3N4Clearance is after 90min
92.7%, hence it is evident that higher than MoO3/C3N4And C3N4, illustrate CDs and MoO3Recombination energy significantly improve the catalytic performance of catalyst.
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, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (9)
1. the preparation method of a kind of carbon point-molybdenum trioxide and nitridation carbon composite photocatalyst, it is characterised in that including following operation
Step：
S1. MoO is prepared3Powder：Weigh seven Ammonium paramolybdate tetrahydrates to be placed in alumina crucible, turn after 60-90 DEG C of temperature heating response
Move in Muffle furnace, and be warming up to 400-550 DEG C and keep the temperature to be calcined；After it is cooled to room temperature, grinding sieving,
Obtain MoO3Powder；
S2. CDs powder is prepared：Urea and citric acid are weighed respectively, adds ultra-pure water, by it by being moved to after ultrasonic dissolution in poly-
Hydro-thermal reaction is carried out in tetrafluoroethene high temperature hydrothermal reaction kettle；Treat that it is cooled to room temperature, obtain the aqueous solution, solution centrifugal is removed
Bulky grain, drying obtain CDs powder after milling；
S3. C is prepared3N4Powder：Weigh cyanamid dimerization to be placed in crucible, and put into Muffle furnace with 2-3 DEG C/min heating rate liters
To 500-600 DEG C and the temperature is kept to be reacted；Taken out after it is cooled to room temperature, grinding sieving obtains C3N4Powder；
S4. MoO is prepared3-CDs/C3N4Composite catalyst：Weigh C3N4Powder, MoO3Powder and the mixing of CDs powder, are added anhydrous
Ethanol, after ultrasonic disperse, the temperature of mixed solution is risen to 75 DEG C and stirring is evaporated, is subsequently moved in baking oven with 100 DEG C of temperature
Drying is spent, takes out powder solid after cooling, grinding is uniform, transfers them in Muffle furnace and is reacted, treats that it is cooled to room
Wen Hou, mill, sieve, obtain carbon point-molybdenum trioxide and nitridation carbon composite photocatalyst.
2. preparation method according to claim 1, it is characterised in that：Heating rate described in step S1 is 2-4 DEG C/min,
The time of the heating response is 10~12h；The time of the calcining is 4~6h；The milling time is 30min.
3. preparation method according to claim 1, it is characterised in that：The mass ratio of urea and citric acid described in step S2
For (0.28~0.50)：1；The temperature of the hydro-thermal reaction is 160-185 DEG C, reaction time 3-5h.
4. preparation method according to claim 1, it is characterised in that：The time reacted described in step S3 is 2-4h.
5. preparation method according to claim 1, it is characterised in that：C described in step S43N4Powder, MoO3Powder and
The mass ratio of CDs powder is 0.9-1.0：0.03-0.05：0.0015-0.003；The time of the ultrasonic disperse is 2-3h；It is described
The time of oven drying is 10-12h；Heating rate is 2-3 DEG C/min in the Muffle furnace, and final temperature is 250-350 DEG C,
The time reacted in Muffle furnace is 4-8h.
6. preparation method according to claim 1, it is characterised in that：Seven Ammonium paramolybdate tetrahydrates described in step S1 are 3-5g；
Urea and citric acid described in step S2 are respectively 1.0-1.5g and 3.0-3.5g, and the addition of the ultra-pure water is using urea as base
Standard, 1g urea add 10ml ultra-pure waters；Cyanamid dimerization described in step S3 is 3-5g；C described in step S43N4Powder, MoO3Powder
It is respectively 0.9-1.0g, 0.03-0.05g and 0.0015-0.003g with CDs powder.
7. carbon point-molybdenum trioxide that a kind of preparation method according to claim 1 is prepared is urged with carbonitride complex light
Agent.
8. carbon point-molybdenum trioxide according to claim 7 is with nitridation carbon composite photocatalyst in field of antibiotics of degrading
Application.
9. application according to claim 8, it is characterised in that：The antibiotic is tetracycline.
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