CN105148968A - Composite photocatalytic material, preparation method and application thereof - Google Patents

Composite photocatalytic material, preparation method and application thereof Download PDF

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CN105148968A
CN105148968A CN201510476768.0A CN201510476768A CN105148968A CN 105148968 A CN105148968 A CN 105148968A CN 201510476768 A CN201510476768 A CN 201510476768A CN 105148968 A CN105148968 A CN 105148968A
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photocatalyst material
composite photocatalyst
composite
dispersion liquid
preparation
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CN105148968B (en
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朱志
逯子扬
闫永胜
霍鹏伟
高乃玲
王友山
姚鑫
黄海
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Jiangsu University
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Jiangsu University
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Abstract

The invention provides a composite photocatalytic material, a preparation method and an application of the composite photocatalytic material. The preparation method comprises: obtaining a precursor of g-C3N4 through high-temperature calcination; preparing a magnetic composite of Fe3O4/g-C3N4 through hydrothermal deposition; and allowing the magnetic composite to react in a solution of silver nitrate through a thermal photodeposition method to obtain the composite photocatalytic material of Ag/Fe3O4/g-C3N4. The composite is high in dispersion and activity, can degrade tetracycline in the environment, and has characteristics of simple synthesis and high degradation rate.

Description

A kind of composite photocatalyst material and its production and use
Technical field
The present invention relates to a kind of photochemical catalyst, refer in particular to a kind of Ag/Fe adopting the hot legal system of high-temperature calcination, hydro-thermal method and light deposition standby 3o 4/ g-C 3n 4composite photocatalyst material and its production and use, belongs to technical field of environmental material preparation.
Background technology
Tetracycline belongs to antibiotics, since appearance, has been applied to clinical successively, and has become application at most, broad-spectrum antibiotic the most widely.But its resistance to the action of a drug and side effect thereof also have a strong impact on the life of people, and the accumulation of long low content is easily developed immunity to drugs simultaneously; Research shows that tetracycline likely affects growth and the formation of tooth, directly threatens the life and health of people.So rationally the antibiotic pharmaceutical wastewater processed in sanitary wastewater is an important link.At present, photocatalysis technology extensive use study the technology of the wastewater treatment in environment.People carry out modification to semiconductor and composite semiconductor and carry out processing environment pollution and obtain good effect, particularly solve the light degradation being only confined to ultraviolet region active, make it effectively can process the pollutant such as waste water, waste gas in life under visible light.
In recent years, g-C 3n 4photocatalytic activity cause the extensive concern of people mainly due to g-C 3n 4there is good chemical stability and directly can utilize the advantages such as visible ray, thus having broad prospects in photochemical catalytic oxidation environmental contaminants etc.But the utilization rate due to its light is low and not recyclable, makes it apply and is restricted.
In order to make up above two shortcomings, (SantoshKumar, SurendarT, BharatKumar, ArabindaBaruah, andVishnuShanker, SynthesisofMagneticallySeparableandRecyclableg-C in existing report 3n 4-Fe 3o 4hybridNanocompositeswithEnhancedPhotocatalyticPerformanc eunderVisible-LightIrradiation, J.Phys.Chem.C2013,117,26135-26143), by Fe 3o 4with carbonitride load, although catalyst can be made to reclaim very well, the photocatalytic activity of composite catalyst effectively can be improved again.But, on the one hand because uneven being difficult to of tri-iron tetroxide dispersion prepares the good composite of pattern, and unstable, and its correlated performance is deteriorated, and photocatalytic activity need to improve on the other hand.Successfully prepare the Fe of high dispersive herein 3o 4/ g-C 3n 4catalysis material, again by Ag successful deposition in Fe 3o 4on.At present, research finds the common participation of the electric conductivity of tri-iron tetroxide and the plasma effect of Ag, defines an electronics and conducts system fast, reaches the effect of cooperative photocatalysis degraded.Accelerate the transfer of light induced electron, also enhance absorption and the utilization of light, improve the right separative efficiency of electronics and hole, greatly facilitate the photocatalytic degradation capability of system.
Summary of the invention
The present invention has considered produced problem in prior art, and object is to provide a kind of high dispersive highly active Ag/Fe 3o 4/ g-C 3n 4composite photocatalyst material and its production and use, this material can be good at tetracycline in degraded environment, has the advantages that synthesis is simple and degradation rate is high.
The technical solution used in the present invention is:
A kind of composite photocatalyst material, be by mass ratio be the Ag of 0.5 ~ 7:3 ~ 20:80 ~ 97, the composite photocatalyst material Ag/Fe that is composited of tri-iron tetroxide and carbonitride 3o 4/ g-C 3n 4.Described composite photocatalyst material Ag/Fe 3o 4/ g-C 3n 4in, g-C 3n 4as prop carrier, Fe 3o 4even particulate dispersion is at g-C 3n 4surface, Ag is deposited on Fe 3o 4surface.
A preparation method for composite photocatalyst material, comprises the steps:
Step 1, preparation g-C 3n 4photochemical catalyst: melamine is placed in porcelain crucible, is placed in Muffle furnace and carries out first time calcining; First time carries out second time calcining after having calcined, product is taken out and porphyrize after room temperature is down in second time calcining end, the product of porphyrize is dispersed in alkaline solution ultrasonic, washing is to neutral again, centrifugation, isolated product is carried out third firing, after room temperature is down in calcining end, takes out product, namely obtains g-C 3n 4photochemical catalyst, saves backup;
Step 2, hydrothermal deposition technology prepare Fe 3o 4/ g-C 3n 4magnetic composite: g-C prepared by step 1 3n 4be scattered in ethylene glycol, ultrasonic disperse, obtain dispersion liquid A; In dispersion liquid A, add Fe(NO3)39H2O, ultrasonic disperse, obtain dispersion liquid B; In dispersion liquid B, add sodium acetate, Macrogol 4000 and polyvinylpyrrolidone (PVP), ultrasonic disperse, obtains dispersion liquid C, loaded by dispersion liquid C in polytetrafluoro water heating kettle, constant temp. heating reacts, and is cooled to room temperature after reaction terminates, washing, suction filtration, vacuum drying, obtains Fe 3o 4/ g-C 3n 4magnetic composite;
Step 3, prepare composite photocatalyst material Ag/Fe 3o 4/ g-C 3n 4: Fe prepared by step 2 3o 4/ g-C 3n 4magnetic composite joins in the deionized water containing silver nitrate, and stirs, and obtains dispersion liquid D, is reacted by dispersion liquid D under uviol lamp; Reaction terminates rear magnet and collects product, and washing, vacuum drying, namely obtains composite photocatalyst material Ag/Fe 3o 4/ g-C 3n 4.
In described step 1, described first time, calcining manners was that constant temperature keeps 2h at 500 DEG C, described second time calcining manners is that constant temperature keeps 2h at 520 DEG C, described third firing mode is that at 150 ~ 300 DEG C, constant temperature keeps 2h, and described first time calcining, second time calcining, third firing heating rate are 2.3 DEG C ~ 4 DEG C/min.
In described step 1, alkaline solution is the sodium hydroxide solution of 1mol/L, and ultrasonic time is 0.5 ~ 1h.
In described step 2, in dispersion liquid C, g-C 3n 4, ethylene glycol, Fe (NO 3) 39H 2o, PVP, PEG and CH 3cOONa3H 2the amount ratio of O is 0.8 ~ 3.0g:20 ~ 40mL:0.05 ~ 0.15g:0.003 ~ 0.007g:0.1 ~ 0.3g:0.5 ~ 1g.
In described step 2, the temperature of constant temp. heating reaction is 190 ~ 200 DEG C, and constant temperature time is 8 ~ 15h.
In described step 3, Fe 3o 4/ g-C 3n 4, silver nitrate, deionized water amount ratio be 0.1-0.6g:0.7-2.1g:10-50mL, the described uviol lamp lower reaction time is 10 ~ 30min.
Described composite photocatalyst material Ag/Fe 3o 4/ g-C 3n 4for photocatalytic degradation tetracycline.
The present invention is utilized to adopt the method for high-temperature calcination to prepare g-C 3n 4and carried magnetic Fe is carried out to it 3o 4modifying and decorating, then carry out surface decorating silver again with light deposition technique, prepare and there is higher catalytic activity and dispersed Ag/Fe 3o 4/ g-C 3n 4composite photo-catalyst.
Technique effect of the present invention is:
(1) the invention describes a kind of callable composite photocatalyst material Ag/Fe of high dispersive 3o 4/ g-C 3n 4and preparation method thereof and application, g-C 3n 4a kind of semiconductor and visible light catalyst of excellent performance, same Fe 3o 4there is excellent conductive performance, Fe 3o 4introducing embody itself and g-C 3n 4synergy, improve photocatalysis effect.Meanwhile, the plasma effect of Ag enhances light absorption and electron transmission, and three's synergy substantially increases photocatalytic speed, and the composite photo-catalyst of high dispersive prepared by the present invention can reach high degradation rate at short notice, can reach 88%; This material also has magnetic, facilitates recycling.
(2) at preparation g-C 3n 4in process, owing to being the preparation method that have employed secondary temperature elevation calcining, make the g-C prepared 3n 4stability is better, and purity is higher, to Fe 3o 4and g-C 3n 4photocatalysis effect after compound advantageously.
(3) suspension characteristic of photochemical catalyst system in Photocatalytic Degradation Process effectively raises the utilization rate to light source.
Accompanying drawing explanation
The projection Electronic Speculum figure of Fig. 1 sample prepared by embodiment 1 and EDX energy spectrogram, wherein (a is g-C 3n 4transmission electron microscope picture, b is Fe 3o 4/ g-C 3n 4transmission electron microscope picture, c is Ag/Fe 3o 4/ g-C 3n 4transmission electron microscope picture, d is Fe 3o 4/ g-C 3n 4eDX can spectrogram;
Fig. 2 is the XRD figure of prepared sample in the embodiment of the present invention, the wherein g-C of a prepared by embodiment 1 3n 4, the Fe of b prepared by embodiment 1 3o 4/ g-C 3n 4, c-g be respectively embodiment 4, embodiment 5, embodiment 1, embodiment 6, embodiment 7 prepare Ag/Fe 3o 4/ g-C 3n 4;
The FT-IR spectrogram of Fig. 3 sample prepared by embodiment 1, wherein a is g-C 3n 4, b is Fe 3o 4/ g-C 3n 4, c is Ag/Fe 3o 4/ g-C 3n 4;
The VSM figure of Fig. 4 sample prepared by embodiment 1, wherein a is Fe 3o 4/ g-C 3n 4, b is Ag/Fe 3o 4/ g-C 3n 4;
The photocurrent curve figure of Fig. 5 sample prepared by embodiment 1, wherein a is g-C 3n 4, b is Fe 3o 4/ g-C 3n 4, c is Ag/Fe 3o 4/ g-C 3n 4;
The Ag/Fe of Fig. 6 prepared by embodiment 1 3o 4/ g-C 3n 4the absorbance change curve in time of degraded tetracycline;
Fig. 7 is the degradation effect figure of prepared sample photocatalytic degradation tetracycline in the embodiment of the present invention, and wherein a is Fe prepared by embodiment 1 3o 4/ g-C 3n 4to the degradation effect curve of tetracycline, b-f is respectively embodiment 4, embodiment 5, embodiment 1, embodiment 6, embodiment 7 are Fe prepared by embodiment 1 3o 4/ g-C 3n 4to the degradation effect curve of tetracycline;
Fig. 8 is Ag/Fe prepared by embodiment 1 3o 4/ g-C 3n 4to photocatalysis 5 circulation experiment figure of tetracycline;
The mechanism schematic diagram of Fig. 9 sample photocatalytic degradation tetracycline prepared by embodiment 1 ~ 7.
Detailed description of the invention
Below in conjunction with concrete embodiment, the invention will be further described:
Embodiment 1:
Step 1, preparation g-C 3n 4photochemical catalyst: crucible put into by the melamine getting 5g purchase, and be placed in Muffle furnace, calcine in air atmosphere, with the ramp of 4 DEG C/min to 500 DEG C, and constant temperature keep 2h, then direct from 500 DEG C with the ramp of 4 DEG C/min to 520 DEG C, and constant temperature keep 2h, naturally cool to room temperature, obtain product; Take out described product and porphyrize, the product of porphyrize is dispersed in ultrasonic 0.5h in alkaline solution, then washing is to neutral, centrifugation, calcines 2h by isolated product at 250 DEG C, takes out product, namely obtain g-C after room temperature is down in calcining end 3n 4photochemical catalyst, saves backup.
Step 2, hydrothermal deposition technology prepare Fe 3o 4/ g-C 3n 4composite: g-C prepared by 1.9g step 1 3n 4be scattered in 30mL ethylene glycol, ultrasonic 20min, add 0.1g Fe(NO3)39H2O again, ultrasonic disperse 20min, then 0.7g sodium acetate is added, the Macrogol 4000 (PEG4000) of 0.2g and the polyvinylpyrrolidone (PVP) of 0.005g, ultrasonic 20 minutes, then load in reactor, put into 200 DEG C of baking ovens, react 12 hours, be cooled to room temperature, respectively wash 3 times with water, absolute ethyl alcohol and (gained solution is poured in beaker from reactor, ultrasonic 20min, use husky star funnel suction filtration again), vacuum 30 DEG C of dryings.Afterwards reactant mixture cooled and use distilled water and absolute alcohol washing for several times.Finally, the sediment Fe obtained 3o 4/ g-C 3n 4drying for standby.
Step 3, prepare composite photocatalyst material Ag/Fe 3o 4/ g-C 3n 4: by 0.3gFe 3o 4/ g-C 3n 4magnetic photocatalyst adds 30mL and stirs to containing in 1.4g silver nitrate deionized water solution, obtains finely disseminated magnetic photocatalytic agent dispersing liquid; Dispersion liquid is carried out reaction 30min under uviol lamp; Reaction terminates rear magnet and collects and use deionized water and absolute ethyl alcohol will obtain composite and respectively wash, and 60 DEG C of vacuum drying chambers oven dry, namely obtain a kind of callable composite photocatalyst material Ag/Fe of high dispersive 3o 4/ g-C 3n 4.
Step 4, the Ag/Fe got in 0.05g step 3 3o 4/ g-C 3n 4joining 100mL contains in the reactor of the 20mg/L tetracycline aqueous solution, and at 30 DEG C, lucifuge stirs and within 40 minutes, reaches adsorption-desorption balance; Open xenon lamp and aeration, sampling in every 15 minutes once, gets 8mL at every turn, the dispersion liquid that Magnetic Isolation is above-mentioned got, and use determined by ultraviolet spectrophotometry absorbance, after absorbance measurement, obtaining the material prepared by the present embodiment after 1.5h to the degradation rate of tetracycline is 88%.
Embodiment 2:
Step 1, preparation g-C 3n 4photochemical catalyst: crucible put into by the melamine getting 5g purchase, and be placed in Muffle furnace, calcine in air atmosphere, with the ramp of 2.3 DEG C/min to 500 DEG C, and constant temperature keep 2h, then direct from 500 DEG C with the ramp of 2.3 DEG C/min to 520 DEG C, and constant temperature keep 2h, naturally cool to room temperature, obtain product; Take out described product and porphyrize, the product of porphyrize is dispersed in ultrasonic 1h in alkaline solution, then washing is to neutral, centrifugation, calcines 2h by isolated product at 150 DEG C, takes out product, namely obtain g-C after room temperature is down in calcining end 3n 4photochemical catalyst, saves backup.
Step 2, hydrothermal deposition technology prepare Fe 3o 4/ g-C 3n 4composite: g-C prepared by 0.8g step 1 3n 4be scattered in 20mL ethylene glycol, ultrasonic 20min, add 0.05g Fe(NO3)39H2O again, ultrasonic disperse 20min, then 0.5g sodium acetate is added, the Macrogol 4000 (PEG4000) of 0.1g and the polyvinylpyrrolidone (PVP) of 0.003g, ultrasonic 20 minutes, then load in reactor, put into 190 DEG C of baking ovens, react 15 hours, be cooled to room temperature, respectively wash 3 times with water, absolute ethyl alcohol and (gained solution is poured in beaker from reactor, ultrasonic 20min, use husky star funnel suction filtration again), vacuum 30 DEG C of dryings.Afterwards reactant mixture cooled and use distilled water and absolute alcohol washing for several times.Finally, the sediment Fe obtained 3o 4/ g-C 3n 4drying for standby.
Step 3, prepare composite photocatalyst material Ag/Fe 3o 4/ g-C 3n 4: by 0.1gFe 3o 4/ g-C 3n 4magnetic photocatalyst adds 10mL and stirs to containing in 0.7g silver nitrate deionized water solution, obtains finely disseminated magnetic photocatalytic agent dispersing liquid; Dispersion liquid is carried out reaction 30min under uviol lamp; Reaction terminates rear magnet and collects and use deionized water and absolute ethyl alcohol will obtain composite and respectively wash, and 60 DEG C of vacuum drying chambers oven dry, namely obtain a kind of callable composite photocatalyst material Ag/Fe of high dispersive 3o 4/ g-C 3n 4.
Step 4, the Ag/Fe got in 0.05g step 3 3o 4/ g-C 3n 4joining 100mL contains in the reactor of the 20mg/L tetracycline aqueous solution, and at 30 DEG C, lucifuge stirs and within 40 minutes, reaches adsorption-desorption balance; Open xenon lamp and aeration, sampling in every 15 minutes once, gets 8mL at every turn, the dispersion liquid that Magnetic Isolation is above-mentioned got, and use determined by ultraviolet spectrophotometry absorbance, after absorbance measurement, obtaining the material prepared by the present embodiment after 1.5h to the degradation rate of tetracycline is 70%.
Embodiment 3:
Step 1, preparation g-C 3n 4photochemical catalyst: crucible put into by the melamine getting 5g purchase, and be placed in Muffle furnace, calcine in air atmosphere, with the ramp of 3 DEG C/min to 500 DEG C, and constant temperature keep 2h, then direct from 500 DEG C with the ramp of 3 DEG C/min to 520 DEG C, and constant temperature keep 2h, naturally cool to room temperature, obtain product; Take out described product and porphyrize, the product of porphyrize is dispersed in ultrasonic 1h in alkaline solution, then washing is to neutral, centrifugation, calcines 2h by isolated product at 300 DEG C, takes out product, namely obtain g-C after room temperature is down in calcining end 3n 4photochemical catalyst, saves backup.
Step 2, hydrothermal deposition technology prepare Fe 3o 4/ g-C 3n 4composite: g-C prepared by 3g step 1 3n 4be scattered in 40mL ethylene glycol, ultrasonic 20min, add 0.15g Fe(NO3)39H2O again, ultrasonic disperse 20min, then 1g sodium acetate is added, the Macrogol 4000 (PEG4000) of 0.3g and the polyvinylpyrrolidone (PVP) of 0.007g, ultrasonic 20 minutes, then load in reactor, put into 200 DEG C of baking ovens, react 8 hours, be cooled to room temperature, respectively wash 3 times with water, absolute ethyl alcohol and (gained solution is poured in beaker from reactor, ultrasonic 20min, use husky star funnel suction filtration again), vacuum 30 DEG C of dryings.Afterwards reactant mixture cooled and use distilled water and absolute alcohol washing for several times.Finally, the sediment Fe obtained 3o 4/ g-C 3n 4drying for standby.
Step 3, prepare composite photocatalyst material Ag/Fe 3o 4/ g-C 3n 4: by 0.6gFe 3o 4/ g-C 3n 4magnetic photocatalyst adds 50mL and stirs to containing in 2.1g silver nitrate deionized water solution, obtains finely disseminated magnetic photocatalytic agent dispersing liquid; Dispersion liquid is carried out reaction 10min under uviol lamp; Reaction terminates rear magnet and collects and use deionized water and absolute ethyl alcohol will obtain composite and respectively wash, and 60 DEG C of vacuum drying chambers oven dry, namely obtain a kind of callable composite photocatalyst material Ag/Fe of high dispersive 3o 4/ g-C 3n 4.
Step 4, the Ag/Fe got in 0.05g step 3 3o 4/ g-C 3n 4joining 100mL contains in the reactor of the 20mg/L tetracycline aqueous solution, and at 30 DEG C, lucifuge stirs and within 40 minutes, reaches adsorption-desorption balance; Open xenon lamp and aeration, sampling in every 15 minutes once, gets 8mL at every turn, the dispersion liquid that Magnetic Isolation is above-mentioned got, and use determined by ultraviolet spectrophotometry absorbance, after absorbance measurement, obtaining the material prepared by the present embodiment after 1.5h to the degradation rate of tetracycline is 66%.
Embodiment 4:
Step 1, preparation g-C 3n 4photochemical catalyst: crucible put into by the melamine getting 5g purchase, and be placed in Muffle furnace, calcine in air atmosphere, with the ramp of 4 DEG C/min to 500 DEG C, and constant temperature keep 2h, then direct from 500 DEG C with the ramp of 4 DEG C/min to 520 DEG C, and constant temperature keep 2h, naturally cool to room temperature, obtain product; Take out described product and porphyrize, the product of porphyrize is dispersed in ultrasonic 0.5h in alkaline solution, then washing is to neutral, centrifugation, calcines 2h by isolated product at 250 DEG C, takes out product, namely obtain g-C after room temperature is down in calcining end 3n 4photochemical catalyst, saves backup.
Step 2, hydrothermal deposition technology prepare Fe 3o 4/ g-C 3n 4composite: g-C prepared by 1.9g step 1 3n 4be scattered in 30mL ethylene glycol, ultrasonic 20min, add 0.1g Fe(NO3)39H2O again, ultrasonic disperse 20min, then 0.7g sodium acetate is added, the Macrogol 4000 (PEG4000) of 0.2g and the polyvinylpyrrolidone (PVP) of 0.005g, ultrasonic 20 minutes, then load in reactor, put into 200 DEG C of baking ovens, react 12 hours, be cooled to room temperature, respectively wash 3 times with water, absolute ethyl alcohol and (gained solution is poured in beaker from reactor, ultrasonic 20min, use husky star funnel suction filtration again), vacuum 30 DEG C of dryings.Afterwards reactant mixture cooled and use distilled water and absolute alcohol washing for several times.Finally, the sediment Fe obtained 3o 4/ g-C 3n 4drying for standby.
Step 3, prepare composite photocatalyst material Ag/Fe 3o 4/ g-C 3n 4: by 0.3gFe 3o 4/ g-C 3n 4magnetic photocatalyst adds 30mL and stirs to containing in 0.7g silver nitrate deionized water solution, obtains finely disseminated magnetic photocatalytic agent dispersing liquid; Dispersion liquid is carried out reaction 30min under uviol lamp; Reaction terminates rear magnet and collects and use deionized water and absolute ethyl alcohol will obtain composite and respectively wash, and 60 DEG C of vacuum drying chambers oven dry, namely obtain a kind of callable composite photocatalyst material Ag/Fe of high dispersive 3o 4/ g-C 3n 4.
Step 4, the Ag/Fe got in 0.05g step 3 3o 4/ g-C 3n 4joining 100mL contains in the reactor of the 20mg/L tetracycline aqueous solution, and at 30 DEG C, lucifuge stirs and within 40 minutes, reaches adsorption-desorption balance; Open xenon lamp and aeration, sampling in every 15 minutes once, gets 8mL at every turn, the dispersion liquid that Magnetic Isolation is above-mentioned got, and use determined by ultraviolet spectrophotometry absorbance, after absorbance measurement, obtaining the material prepared by the present embodiment after 1.5h to the degradation rate of tetracycline is 47%.
Embodiment 5:
Step 1, preparation g-C 3n 4photochemical catalyst: crucible put into by the melamine getting 5g purchase, and be placed in Muffle furnace, calcine in air atmosphere, with the ramp of 4 DEG C/min to 500 DEG C, and constant temperature keep 2h, then direct from 500 DEG C with the ramp of 4 DEG C/min to 520 DEG C, and constant temperature keep 2h, naturally cool to room temperature, obtain product; Take out described product and porphyrize, the product of porphyrize is dispersed in ultrasonic 0.5h in alkaline solution, then washing is to neutral, centrifugation, calcines 2h by isolated product at 250 DEG C, takes out product, namely obtain g-C after room temperature is down in calcining end 3n 4photochemical catalyst, saves backup.
Step 2, hydrothermal deposition technology prepare Fe 3o 4/ g-C 3n 4composite: g-C prepared by 1.9g step 1 3n 4be scattered in 30mL ethylene glycol, ultrasonic 20min, add 0.1g Fe(NO3)39H2O again, ultrasonic disperse 20min, then 0.7g sodium acetate is added, the Macrogol 4000 (PEG4000) of 0.2g and the polyvinylpyrrolidone (PVP) of 0.005g, ultrasonic 20 minutes, then load in reactor, put into 200 DEG C of baking ovens, react 12 hours, be cooled to room temperature, respectively wash 3 times with water, absolute ethyl alcohol and (gained solution is poured in beaker from reactor, ultrasonic 20min, use husky star funnel suction filtration again), vacuum 30 DEG C of dryings.Afterwards reactant mixture cooled and use distilled water and absolute alcohol washing for several times.Finally, the sediment Fe obtained 3o 4/ g-C 3n 4drying for standby.
Step 3, prepare composite photocatalyst material Ag/Fe 3o 4/ g-C 3n 4: by 0.3gFe 3o 4/ g-C 3n 4magnetic photocatalyst adds 30mL and stirs to containing in 1g silver nitrate deionized water solution, obtains finely disseminated magnetic photocatalytic agent dispersing liquid; Dispersion liquid is carried out reaction 30min under uviol lamp; Reaction terminates rear magnet and collects and use deionized water and absolute ethyl alcohol will obtain composite and respectively wash, and 60 DEG C of vacuum drying chambers oven dry, namely obtain a kind of callable composite photocatalyst material Ag/Fe of high dispersive 3o 4/ g-C 3n 4.
Step 4, the Ag/Fe got in 0.05g step 3 3o 4/ g-C 3n 4joining 100mL contains in the reactor of the 20mg/L tetracycline aqueous solution, and at 30 DEG C, lucifuge stirs and within 40 minutes, reaches adsorption-desorption balance; Open xenon lamp and aeration, sampling in every 15 minutes once, gets 8mL at every turn, the dispersion liquid that Magnetic Isolation is above-mentioned got, and use determined by ultraviolet spectrophotometry absorbance, after absorbance measurement, obtaining the material prepared by the present embodiment after 1.5h to the degradation rate of tetracycline is 52%.
Embodiment 6:
Step 1, preparation g-C 3n 4photochemical catalyst: crucible put into by the melamine getting 5g purchase, and be placed in Muffle furnace, calcine in air atmosphere, with the ramp of 4 DEG C/min to 500 DEG C, and constant temperature keep 2h, then direct from 500 DEG C with the ramp of 4 DEG C/min to 520 DEG C, and constant temperature keep 2h, naturally cool to room temperature, obtain product; Take out described product and porphyrize, the product of porphyrize is dispersed in ultrasonic 0.5h in alkaline solution, then washing is to neutral, centrifugation, calcines 2h by isolated product at 250 DEG C, takes out product, namely obtain g-C after room temperature is down in calcining end 3n 4photochemical catalyst, saves backup.
Step 2, hydrothermal deposition technology prepare Fe 3o 4/ g-C 3n 4composite: g-C prepared by 1.9g step 1 3n 4be scattered in 30mL ethylene glycol, ultrasonic 20min, add 0.1g Fe(NO3)39H2O again, ultrasonic disperse 20min, then 0.7g sodium acetate is added, the Macrogol 4000 (PEG4000) of 0.2g and the polyvinylpyrrolidone (PVP) of 0.005g, ultrasonic 20 minutes, then load in reactor, put into 200 DEG C of baking ovens, react 12 hours, be cooled to room temperature, respectively wash 3 times with water, absolute ethyl alcohol and (gained solution is poured in beaker from reactor, ultrasonic 20min, use husky star funnel suction filtration again), vacuum 30 DEG C of dryings.Afterwards reactant mixture cooled and use distilled water and absolute alcohol washing for several times.Finally, the sediment Fe obtained 3o 4/ g-C 3n 4drying for standby.
Step 3, prepare composite photocatalyst material Ag/Fe 3o 4/ g-C 3n 4: by 0.3gFe 3o 4/ g-C 3n 4magnetic photocatalyst adds 30mL and stirs to containing in 1.8g silver nitrate deionized water solution, obtains finely disseminated magnetic photocatalytic agent dispersing liquid; Dispersion liquid is carried out reaction 30min under uviol lamp; Reaction terminates rear magnet and collects and use deionized water and absolute ethyl alcohol will obtain composite and respectively wash, and 60 DEG C of vacuum drying chambers oven dry, namely obtain a kind of callable composite photocatalyst material Ag/Fe of high dispersive 3o 4/ g-C 3n 4.
Step 4, the Ag/Fe got in 0.05g step 3 3o 4/ g-C 3n 4joining 100mL contains in the reactor of the 20mg/L tetracycline aqueous solution, and at 30 DEG C, lucifuge stirs and within 40 minutes, reaches adsorption-desorption balance; Open xenon lamp and aeration, sampling in every 15 minutes once, gets 8mL at every turn, the dispersion liquid that Magnetic Isolation is above-mentioned got, and use determined by ultraviolet spectrophotometry absorbance, after absorbance measurement, obtaining the material prepared by the present embodiment after 1.5h to the degradation rate of tetracycline is 77%.
Embodiment 7:
Step 1, preparation g-C 3n 4photochemical catalyst: crucible put into by the melamine getting 5g purchase, and be placed in Muffle furnace, calcine in air atmosphere, with the ramp of 4 DEG C/min to 500 DEG C, and constant temperature keep 2h, then direct from 500 DEG C with the ramp of 4 DEG C/min to 520 DEG C, and constant temperature keep 2h, naturally cool to room temperature, obtain product; Take out described product and porphyrize, the product of porphyrize is dispersed in ultrasonic 0.5h in alkaline solution, then washing is to neutral, centrifugation, calcines 2h by isolated product at 250 DEG C, takes out product, namely obtain g-C after room temperature is down in calcining end 3n 4photochemical catalyst, saves backup.
Step 2, hydrothermal deposition technology prepare Fe 3o 4/ g-C 3n 4composite: g-C prepared by 1.9g step 1 3n 4be scattered in 30mL ethylene glycol, ultrasonic 20min, add 0.1g Fe(NO3)39H2O again, ultrasonic disperse 20min, then 0.7g sodium acetate is added, the Macrogol 4000 (PEG4000) of 0.2g and the polyvinylpyrrolidone (PVP) of 0.005g, ultrasonic 20 minutes, then load in reactor, put into 200 DEG C of baking ovens, react 12 hours, be cooled to room temperature, respectively wash 3 times with water, absolute ethyl alcohol and (gained solution is poured in beaker from reactor, ultrasonic 20min, use husky star funnel suction filtration again), vacuum 30 DEG C of dryings.Afterwards reactant mixture cooled and use distilled water and absolute alcohol washing for several times.Finally, the sediment Fe obtained 3o 4/ g-C 3n 4drying for standby.
Step 3, prepare composite photocatalyst material Ag/Fe 3o 4/ g-C 3n 4: by 0.3gFe 3o 4/ g-C 3n 4magnetic photocatalyst adds 30mL and stirs to containing in 2.1g silver nitrate deionized water solution, obtains finely disseminated magnetic photocatalytic agent dispersing liquid; Dispersion liquid is carried out reaction 30min under uviol lamp; Reaction terminates rear magnet and collects and use deionized water and absolute ethyl alcohol will obtain composite and respectively wash, and 60 DEG C of vacuum drying chambers oven dry, namely obtain a kind of callable composite photocatalyst material Ag/Fe of high dispersive 3o 4/ g-C 3n 4.
Step 4, the Ag/Fe got in 0.05g step 3 3o 4/ g-C 3n 4joining 100mL contains in the reactor of the 20mg/L tetracycline aqueous solution, and at 30 DEG C, lucifuge stirs and within 40 minutes, reaches adsorption-desorption balance; Open xenon lamp and aeration, sampling in every 15 minutes once, gets 8mL at every turn, the dispersion liquid that Magnetic Isolation is above-mentioned got, and use determined by ultraviolet spectrophotometry absorbance, after absorbance measurement, obtaining the material prepared by the present embodiment after 1.5h to the degradation rate of tetracycline is 60%.
Photocatalytic activity evaluation: carry out in DW-01 type photochemical reaction instrument, visible lamp irradiates, 100mL20mg/L tetracycline simulated wastewater to be added in reactor and to measure its initial value, then photochemical catalyst is added, magnetic agitation and open aerator pass into air keep catalyst be in suspension or afloat, sample after dark adsorption equilibrium, 10min sample analysis in interval in During Illumination, gets supernatant liquor at spectrophotometer λ after centrifugation max=357nm place measures absorbance, and passes through formula: DC=[(C 0-C i)/C 0] × 100% calculates degradation rate, wherein C 0the absorbance of tetracycline during for reaching adsorption equilibrium, C iwhat measure for timing sampling is the absorbance of tetracycline.
G-C 3n 4photochemical catalyst, Fe 3o 4/ g-C 3n 4photochemical catalyst, Ag/Fe 3o 4/ g-C 3n 4the TEM of composite photo-catalyst schemes as shown in Figure 1, as seen from the figure, and g-C 3n 4surface is through overload Fe 3o 4surface uniform is distributed with more Fe 3o 4particle and high degree of dispersion, still well maintain g-C after Ag modifying and decorating 3n 4lamellar structure and Fe 3o 4spherical structure; In addition as can be seen from the ratio in figure also, Ag has optionally been modified at Fe 3o 4surface.
G-C 3n 4photochemical catalyst, Fe 3o 4/ g-C 3n 4the X diffraction pattern of photochemical catalyst, surface molecule print composite photo-catalyst as shown in Figure 2, as can be seen from the figure g-C 3n 4characteristic diffraction peak 2 θ=27.4 °, 13.1 ° are corresponding with standard card.This photochemical catalyst sample g-C is described 3n 4prepared by success; And through Fe 3o 4the g-C of load 3n 4in catalyst, g-C 3n 4characteristic peak not do not change, there is obvious Fe simultaneously 3o 4characteristic peak in 2 θ=30.2 °, 35.5 °, 43.2 °, 53.4,57.3 °, 62.6 °.After Ag modifies, the g-C in figure 3n 4characteristic diffraction peak not change.And Fe 3o 4characteristic diffraction peak along with Ag addition increase and die down, illustrate that Ag is selective and be deposited on Fe 3o 4surface.
G-C 3n 4photochemical catalyst, Fe 3o 4/ g-C 3n 4photochemical catalyst, Ag/Fe 3o 4/ g-C 3n 4as shown in Figure 3, as can be seen from the figure peak is a series of appears at 1650cm to the FT-IR spectrogram of composite photo-catalyst -1~ 1200cm -1(1251,1325,1419,1571, and 1639cm -1) the CN heterocyclic compound of respectively corresponding typical stretch mode, such as C-N and C=N stretching vibration, at 808cm -1near be the position at typical 5-triazine units peak.At 3400cm -1~ 2800cm -1left and right is-NH 2skeletal vibration absworption peak.Can see that the introducing along with Ag does not affect Fe in the FT-IR spectrogram of composite photo-catalyst 3o 4/ g-C 3n 4the peak intensity of photochemical catalyst.This also illustrates Ag and be successfully modified at Fe 3o 4surface.
Fe 3o 4/ g-C 3n 4photochemical catalyst, Ag/Fe 3o 4/ g-C 3n 4the VSM spectrogram of composite photo-catalyst, as can be seen from Figure 4, Fe 3o 4/ g-C 3n 4, Ag/Fe 3o 4/ g-C 3n 4the magnetic saturation angle value of composite photo-catalyst is respectively 16.8emu/g and 12.68emu/g.By analysis, the reason that intensity value reduces is because the covering of Ag causes.But can find out that under the effect of externally-applied magnetic field composite photo-catalyst still can fully be collected from diagram, so this catalyst after a procedure or can be essentially completely recovered utilization.
Ag/Fe 3o 4/ g-C 3n 4composite photo-catalyst photocurrent-time curve as shown in Figure 5, as can be seen from the figure, g-C 3n 4, Fe 3o 4/ g-C 3n 4, Ag/Fe 3o 4/ g-C 3n 4photo-current intensity strengthen gradually, this also demonstrates Fe 3o 4enhance the electric conductivity of composite with the introducing of Ag, thus promote electron hole separation, improve further the degradation effect to tetracycline.
Ag/Fe 3o 4/ g-C 3n 4as shown in Figure 6, as can be seen from the figure along with the increase of time, the characteristic peak of tetracycline is weakening the absorbance of composite photocatalyst for degrading tetracycline gradually, and this illustrates that tetracycline is at other materials of generation that are constantly degraded.
Fig. 7 is the photocatalysis effect figure of prepared sample to tetracycline, illustrates: in preparation process, add Fe 3o 4/ g-C 3n 4, silver nitrate, deionized water amount ratio be 0.3g:1.4g:30mL, prepared composite photo-catalyst has best degradation effect, and degradation rate is high, and in 1.5h, degradation rate reaches 88%.In composite, Ag and Fe 3o 4embodiment very little, is not gone out Ag and Fe by content 3o 4advantageous property, therefore, photocatalysis effect is unsatisfactory; On the other hand, be not Ag and Fe 3o 4the more the better, because Ag and Fe 3o 4content is too high, will embed g-C 3n 4, photocatalysis effect is declined.
Ag/Fe 3o 4/ g-C 3n 45 circulation experiment figure of composite photo-catalyst as shown in Figure 8, as can be seen from the figure, catalyst does not almost go down in its catalytic activity after 5 recyclings, illustrate that catalyst has good stability, illustrates that this composite photo-catalyst has certain potential using value in the pollution controls such as industrial wastewater on the other hand on the one hand.
Ag/Fe 3o 4/ g-C 3n 4the catalytic mechanism of composite photo-catalyst is as shown in Figure 9: on the one hand, when composite photo-catalyst is under visible light exposure, g-C 3n 4be easy to absorb visible ray.Ag and Fe 3o 4outstanding electronic conductor, and under promoting the radiation of visible light of electronics from ground state to excitation state.Electronics is from g-C 3n 4valence band be excited to conduction band and leave hole.In addition, g-C 3n 4hole be transferred to the surface of PPy, the recombination rate of the electron hole pair of compound system is significantly reduced raising photocatalytic activity.On the other hand, due to the surface plasma effect effect of Ag, enhance the absorption of light, reach the object removing target contaminant further.
Described embodiment is preferred embodiment of the present invention; but the present invention is not limited to above-mentioned embodiment; when not deviating from flesh and blood of the present invention, any apparent improvement that those skilled in the art can make, replacement or modification all belong to protection scope of the present invention.

Claims (8)

1. a composite photocatalyst material, is characterized in that, described composite photocatalyst material be by mass ratio be the Ag of 0.5 ~ 7:3 ~ 20:80 ~ 97, the composite photocatalyst material Ag/Fe that is composited of tri-iron tetroxide and carbonitride 3o 4/ g-C 3n 4.Described composite photocatalyst material Ag/Fe 3o 4/ g-C 3n 4in, g-C 3n 4as prop carrier, Fe 3o 4even particulate dispersion is at g-C 3n 4surface, Ag is deposited on Fe 3o 4surface.
2. the preparation method of a kind of composite photocatalyst material according to claim 1, is characterized in that, comprise the steps:
Step 1, preparation g-C 3n 4photochemical catalyst: melamine is placed in porcelain crucible, is placed in Muffle furnace and carries out first time calcining; First time carries out second time calcining after having calcined, product is taken out and porphyrize after room temperature is down in second time calcining end, the product of porphyrize is dispersed in alkaline solution ultrasonic, washing is to neutral again, centrifugation, isolated product is carried out third firing, after room temperature is down in calcining end, takes out product, namely obtains g-C 3n 4photochemical catalyst, saves backup;
Step 2, hydrothermal deposition technology prepare Fe 3o 4/ g-C 3n 4magnetic composite: g-C prepared by step 1 3n 4be scattered in ethylene glycol, ultrasonic disperse, obtain dispersion liquid A; In dispersion liquid A, add Fe(NO3)39H2O, ultrasonic disperse, obtain dispersion liquid B; In dispersion liquid B, add sodium acetate, Macrogol 4000 and polyvinylpyrrolidone (PVP), ultrasonic disperse, obtains dispersion liquid C, loaded by dispersion liquid C in polytetrafluoro water heating kettle, constant temp. heating reacts, and is cooled to room temperature after reaction terminates, washing, suction filtration, vacuum drying, obtains Fe 3o 4/ g-C 3n 4magnetic composite;
Step 3, prepare composite photocatalyst material Ag/Fe 3o 4/ g-C 3n 4: Fe prepared by step 2 3o 4/ g-C 3n 4magnetic composite joins in the deionized water containing silver nitrate, and stirs, and obtains dispersion liquid D, is reacted by dispersion liquid D under uviol lamp; Reaction terminates rear magnet and collects product, and washing, vacuum drying, namely obtains composite photocatalyst material Ag/Fe 3o 4/ g-C 3n 4.
3. the preparation method of a kind of composite photocatalyst material according to claim 2, it is characterized in that, in step 1, described first time, calcining manners was that constant temperature keeps 2h at 500 DEG C, described second time calcining manners is that constant temperature keeps 2h at 520 DEG C, and described third firing mode is that at 150 ~ 300 DEG C, constant temperature keeps 2h; Described first time calcining, second time calcining, third firing heating rate are 2.3 DEG C ~ 4 DEG C/min.
4. the preparation method of a kind of composite photocatalyst material according to claim 2, is characterized in that, in step 1, alkaline solution is the sodium hydroxide solution of 1mol/L, and ultrasonic time is 0.5 ~ 1h.
5. the preparation method of a kind of composite photocatalyst material according to claim 2, is characterized in that, in step 2, in dispersion liquid C, and g-C 3n 4, ethylene glycol, Fe (NO 3) 39H 2o, PVP, PEG and CH 3cOONa3H 2the amount ratio of O is 0.8 ~ 3.0g:20 ~ 40mL:0.05 ~ 0.15g:0.003 ~ 0.007g:0.1 ~ 0.3g:0.5 ~ 1g.
6. the preparation method of a kind of composite photocatalyst material according to claim 2, is characterized in that, in step 2, the temperature of constant temp. heating reaction is 190 ~ 200 DEG C, and constant temperature time is 8 ~ 15h.
7. the preparation method of a kind of composite photocatalyst material according to claim 2, is characterized in that, in step 3, and Fe 3o 4/ g-C 3n 4, silver nitrate, deionized water amount ratio be 0.1 ~ 0.6g:0.7 ~ 2.1g:10 ~ 50mL, the described uviol lamp lower reaction time is 10 ~ 30min.
8. the purposes of a kind of composite photocatalyst material according to claim 1, is characterized in that, described composite photocatalyst material is used for photocatalytic degradation tetracycline.
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