CN107262134A - A kind of novel magnetic multifunctional photocatalysis material and its preparation method and application - Google Patents
A kind of novel magnetic multifunctional photocatalysis material and its preparation method and application Download PDFInfo
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- CN107262134A CN107262134A CN201710655306.4A CN201710655306A CN107262134A CN 107262134 A CN107262134 A CN 107262134A CN 201710655306 A CN201710655306 A CN 201710655306A CN 107262134 A CN107262134 A CN 107262134A
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- 239000000463 material Substances 0.000 title claims abstract description 61
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 53
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 30
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims abstract description 26
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 24
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 18
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 235000011187 glycerol Nutrition 0.000 claims abstract description 15
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001868 water Inorganic materials 0.000 claims abstract description 13
- 238000011084 recovery Methods 0.000 claims abstract description 9
- 238000005286 illumination Methods 0.000 claims abstract description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 30
- 230000015556 catabolic process Effects 0.000 claims description 19
- 238000006731 degradation reaction Methods 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 238000002474 experimental method Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 230000008859 change Effects 0.000 claims description 10
- 239000003643 water by type Substances 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002835 absorbance Methods 0.000 claims description 8
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 230000004044 response Effects 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004809 Teflon Substances 0.000 claims description 5
- 229920006362 Teflon® Polymers 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 238000004364 calculation method Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000005259 measurement Methods 0.000 claims description 5
- 150000007974 melamines Chemical class 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 229910052573 porcelain Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000002798 spectrophotometry method Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000000523 sample Substances 0.000 claims description 2
- 239000012488 sample solution Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 239000000598 endocrine disruptor Substances 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 230000004043 responsiveness Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229940011871 estrogen Drugs 0.000 description 2
- 239000000262 estrogen Substances 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000704 bioconcentration Toxicity 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- 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
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a kind of preparation method of novel magnetic multifunctional photocatalysis material, using melamine as raw material, HCl, glycerine and H are added2Centrifugal drying after O stirrings, 1 ~ 3 is heated in Muffle furnace, g C are produced after cooling3N4；Then FeCl is added in aqueous2·4H2O, AgNO3And PVP（Polyvinylpyrrolidone）, novel magnetic catalysis material Ag Fe are made by one step hydro thermal method3O4/g‑C3N4.The novel magnetic multifunctional photocatalysis material that the present invention is provided, wherein Ag doping enhances responsiveness of the material for visible ray, optimizes photocatalysis performance, Fe3O4Doping make the present invention strong magnet attraction under can be separated with solution, improve the material yield rate and cyclic utilization rate；Under visible light illumination, photocatalytic water can be catalyzed and prepares hydrogen, also have good catalytic action to degraded Typical Endocrine Disrupting Chemicals octyl phenol；The preparation technology for the catalysis material that the present invention is provided is simple, raw material high conversion rate, and recovery utilization rate is high, non-secondary pollution.
Description
Technical field
The present invention relates to a kind of novel magnetic multifunctional photocatalysis material and its preparation method and application, belong to photocatalysis material
Expect technical field.
Background technology
In recent years, with the lifting of industrial expansion and social economy's level, all kinds of chemistry is flooded with people's life and are used
Product, more and more artificial synthesized new organic pollutions are detected in natural water, and the balance to ecological environment is caused
Serious harm.Wherein, estrogens environment incretion interferent octyl phenol is commonly used as conventional fine chemical material
In the production of the products such as nonionic surfactant, antioxidant, coating, rubber.Because of its lipophilic, bioconcentration and cause
The a series of characteristic such as carcinous, huge harm can be also caused even if micro presence to human health.Except environmental area, people
Increasing challenge is also faced in energy field.Fossil fuel it is non-renewable, people is thrown to sight newly
Renewable and clean energy resource on, wherein, Hydrogen Energy is exactly one of focus for studying at this stage.
Photocatalysis technology with its efficiently, energy-conservation, stably, harmless and environmental protection the advantages of become the focus of research.Light
Catalysis technique is to absorb luminous energy by the use of semiconductor as photochemical catalyst, generates photo-generate electron-hole pair, and then to being adsorbed in surface
Pollutant directly carry out redox.And current many study limitations for photochemical catalyst limit in ultraviolet light
For the utilization of visible ray solar energy.Polymeric organic semiconductors g-C3N4With suitable band gap, it can be produced in visible-range
The third contact of a total solar or lunar eclipse gives birth to electron-hole pair, directly organic pollutant can be decomposed under sunshine irradiation, while can be in visible ray
The lower photocatalytic water of irradiation produces hydrogen, and its multifunctionality obtains the extensive concern of people.Efficient g-C3N4The research and development of photochemical catalyst
It is to realize one of key that new organic pollution polluted water is repaired.And pure g-C3N4Still suffering from one in catalytic reaction process is
The deficiency of row：
First, in conventional g-C3N4In preparation method, often with melamine, dicyandiamide etc. for nitrogen source, obtained by heating polymerization
To g-C3N4 , but it is heated, labile characteristic causes g-C3N4Low yield, waste of raw materials is serious；
2nd, the g-C of heating polymerization generation3N4Specific surface area is smaller, and material pore structure is unstable, with presoma, heating temperature
Degree etc. the influence of factor and change, influence catalytic efficiency；
3rd, the estrogens incretion interferent concentration in environment is low, and degraded difficulty is big, pure g-C3N4Under excited by visible light
The electron hole of generation is easily combined, and causes degradation effect poor, photocatalysis efficiency is low；
4th, the powdered g-C in suspension system3N4Catalyst is difficult to reclaim, and makes the loss of photochemical catalyst serious, while also easily making
Into secondary pollution.
The content of the invention
Purpose：In order to overcome the deficiencies in the prior art, the present invention provides a kind of preparation technology simply, and photocatalysis is lived
Property it is high, stability is high, it is easy to separated with solution, and recovery utilization rate is high, non-secondary pollution, and can degrade new organic pollution
Novel magnetic catalysis material.
Technical scheme：In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of preparation method of novel magnetic multifunctional photocatalysis material, comprises the following steps：
S1. appropriate melamine, HCl solution, glycerine, deionized water are taken, is mutually mixed and 10 ~ 30min is stirred at room temperature, from
Heart filtration drying；Melamine by pretreatment is placed in porcelain crucible with cover, heated in Muffle furnace, the temperature of Muffle furnace is first
200 ~ 250 DEG C are warming up to 2 ~ 4 DEG C/min speed, then 500 ~ 550 DEG C, keeping temperature are warming up to 5 ~ 10 DEG C/min speed
Heat 1 ~ 3h；After heating terminates, room temperature is naturally cooled to, faint yellow product g-C is collected3N4And grind into powder is stand-by；
S2. g-C made from appropriate step S1 is taken3N4It is scattered in 50ml deionized waters, 0.5 ~ 2h of ultrasonic oscillation；
S3. appropriate FeCl is added in the aqueous solution in step s 22·4H2O, AgNO3With PVP（Polyvinylpyrrolidone）, stir
Mix after 2.5 ~ 4h, take appropriate ammonia solution to add in foregoing mixed solution, while being stirred vigorously 5 ~ 15min, make Fe (II) fully oxygen
Change；
S4. the obtained suspension of step S3 is transferred in the autoclave of 50ml teflon seals and added at 130 ~ 150 DEG C
2.5 ~ 3.5h of heat；
S5. after question response terminates and cooled down, autoclave is taken out, products therefrom is washed 3 times with distilled water and absolute ethyl alcohol respectively
Afterwards, 12 ~ 13h is dried at 80 ~ 100 DEG C of baking oven, product Ag-Fe is obtained3O4/g-C3N4 。
Wherein, melamine, HCl solution, glycerine and H in the step S12O specifically used amount is：3~5g melamines, 10 ~
20ml HCl, 5 ~ 10ml glycerine, 2 ~ 5ml H2O。
Wherein, the FeCl in the step S32·4H2O, AgNO3With PVP（Polyvinylpyrrolidone）Specific addition
For：0.3g~0.6g FeCl2·4H2O, 20~35mg AgNO3, 0.1~0.2g PVP（Polyvinylpyrrolidone）.
Wherein, the mass concentration of ammonia solution is 25 ~ 28% in the step S3, and addition is 2 ~ 3.5ml.
A kind of novel magnetic multifunctional photocatalysis material, using the preparation side of foregoing novel magnetic multifunctional photocatalysis material
Method is made.
Before a kind of application of novel magnetic multifunctional photocatalysis material, wherein novel magnetic multifunctional photocatalysis material are used
The preparation method for the novel magnetic multifunctional photocatalysis material stated is made, and the application includes catalysis material in degraded octyl phenol
In application and catalysis material catalysis photocatalytic water prepare hydrogen in application.
Wherein, application of the catalysis material in degraded octyl phenol comprises the following steps：
（1）By 50mg photochemical catalysts Ag-Fe3O4/g-C3N4It is that the octyl phenol that 20ppm, volume are 100ml is molten to add initial concentration
In liquid, mixing suspension is formed；
（2）Foregoing mixing suspension under visible light illumination while carry out magnetic agitation, every 30min take out 1ml samples, lead to
Cross catalyst remaining in centrifugally operated removal sample and obtain solution；
（3）Spectrophotometry instrument is used to detect the absorbance of sample solution to calculate octyl phenol concentration；
（4）Complete step（1）Arrive（3）Operation be degradation experiment, often carry out three degradation experiments, reclaimed by strong magnet
Photochemical catalyst, and the rate of recovery of survey calculation photochemical catalyst；The octyl group of the equal initial concentration all more renewed is tested every time
Phenol solution.
Further, step（2）In visible ray light source be equipped with visible ray filter plate（The nm of Bo Chang≤400）10
~30 W daily LED.
Wherein, application of the catalysis material in catalysis photocatalytic water prepares hydrogen comprises the following steps：
（1）Take 50mg photochemical catalysts Ag-Fe3O4/g-C3N4Add in 100ml deionized waters, contain 10% in the deionized water
The glycerine of volume fraction；
（2）3 ~ 5min of ultrasonic disperse, it is in suspension system to make solution；
（3）1 ~ 3h is irradiated under visible light, and the light source of the visible ray is equipped with visible ray filter plate（The nm of Bo Chang≤400）'s
200 ~ 400W day lamps；
（4）By gas chromatographic measurement hydrogen output, a data are recorded every 30min.
Beneficial effect：The preparation method for the novel magnetic multifunctional photocatalysis material that the present invention is provided, using simple one
One-step hydrothermal, synthesizes a kind of novel magnetic catalysis material Ag-Fe3O4/g-C3N4 , process is simple to operate, efficiency high,
Equipment requirement is low；Gained ternary nano composite material Ag-Fe3O4/g-C3N4Purity is high, catalytic performance is good, and Ag doping is accelerated
The separation of electron hole, makes catalysis material increase for visible light-responded scope, solves pure g-C3N4Electron hole is easily combined
The problem of, optimize photocatalysis performance, Fe3O4Doping make catalysis material that there is ferromagnetism, can be with strong magnet attraction
Solution is separated, and the rate of recovery and cyclic utilization rate of catalysis material is improved, while Fe3O4The characteristic of low band gaps also improves light
Degradation efficiency.The present invention has expanded novel magnetic catalysis material Ag-Fe3O4/g-C3N4On new organic pollutant degradation
Sewage repair the application of field and the new energy field on Hydrogen Energy.
From preparation method and application as can be seen that the novel magnetic catalysis material that the present invention is provided has following advantage：
1st, selection melamine is as raw material, by the pretreatment to melamine, improves product g-C3N4Void ratio, strengthens its photocatalysis
Performance；
2nd, novel magnetic catalysis material Ag-Fe3O4/g-C3N4Prepared by one step hydro thermal method, processing step is simplified, equipment will
Ask low, workable, preparation efficiency is greatly improved；
3rd, novel magnetic catalysis material Ag-Fe3O4/g-C3N4Pass through Ag and Fe3O4To g-C3N4Modification, change g-C3N4Table
Surface properties, expand its response range for visible ray, enhance photocatalytic activity, improve the degraded effect for octyl phenol
Rate, can effectively remove trace incretion interferent；
4、g-C3N4For inert material, catalyst stability height will not be corroded or divide under strong acid and strong base and 600 degree of high temperature
Solution, catalyst stability is strong；
5、Fe3O4Have magnetic material as one kind, its adulterate allow the novel photocatalysis material by strong magnet with it is molten
Liquid is separated, and catalyst recovery yield is high, repeats utilization rate height, and will not cause secondary pollution.
6th, the novel magnetic multifunctional photocatalysis material that the present invention is provided is also equipped with photodissociation excellent under visible light illumination
H2-producing capacity.
Brief description of the drawings
Fig. 1 is Ag-Fe prepared by embodiment 13O4/g-C3N4Field emission scanning electron microscope FESEM figure；
Fig. 2 is Ag-Fe prepared by embodiment 13O4/g-C3N4Transmission electron microscope TEM figure；
Fig. 3 is to have modified Ag-Fe3O4With unmodified Ag-Fe3O4Class graphitic nitralloy carbon g-C3N4Degraded with the time to octyl phenol
Contrast on effect block diagram.
Fig. 4 is Ag-Fe in embodiment 13O4/g-C3N4To in the degradation experiment of octyl phenol, solution absorbance with the time change
Change curve map.
Embodiment
The present invention is further described below in conjunction with the accompanying drawings.
Embodiment 1
Novel magnetic multifunctional photocatalysis material is prepared, step is as follows：
S1. 4g melamines, 15ml HCl, 10ml glycerine, 3ml H are taken2O, is stirred after 30min at room temperature, and centrifugal filtration is dried.
Melamine by pretreatment is placed in porcelain crucible with cover, 220 DEG C are heated in Muffle furnace（4 DEG C/min of heating rate）, connect
And be heated to 550 DEG C（Heating rate is 8 DEG C/min）1.5h.After end, room temperature is naturally cooled to, faint yellow product g- is collected
C3N4And grind into powder is stand-by；
S2. g-C made from 60mg steps S1 is taken3N4It is placed in 50ml deionized waters, ultrasonic oscillation 1.5h；
S3. 0.6g FeCl are continuously added2·4H2O, 35mg AgNO3With 0.15g PVP, stir after 3.5h, take 3.5ml mass
Concentration makes Fe (II) fully oxidized to be stirred vigorously 10min simultaneously in 27% ammonia solution addition mixed solution；
S4. suspension is transferred in the autoclave of 50ml teflon seals and heats 3.0h at 135 DEG C；
S5. question response terminates after cooling, takes out autoclave, products therefrom is washed 3 times with distilled water and absolute ethyl alcohol respectively
Afterwards, 12h is dried at 90 DEG C in an oven, obtain Ag-Fe3O4/g-C3N4 .The Ag-Fe prepared3O4/g-C3N4Flied emission
SEM FESEM is schemed as shown in figure 1, Ag-Fe3O4/g-C3N4Transmission electron microscope TEM figures it is as shown in Figure 2.
Application of the novel magnetic multifunctional photocatalysis material in degraded octyl phenol, comprises the following steps：
（1）In being the octyl group phenol solution that 20ppm volumes are 100ml by 50mg photochemical catalysts addition initial concentration；
（2）Using equipped with visible ray filter plate（The nm of Bo Chang≤400）20 W daily LED as visible ray light source, mix
Magnetic agitation is carried out while closing liquid under visible light illumination, 1ml samples are taken out by centrifuging the remaining catalysis of removal every 30min
Agent obtains solution；
（3）Spectrophotometry instrument is used to survey its absorbance to detect the change of octyl phenol concentration；Refering to Fig. 3, modification
Ag-Fe3O4With unmodified Ag-Fe3O4Class graphitic nitralloy carbon g-C3N4The degradation effect of octyl phenol is contrasted with the time, tied
Fruit shows, has modified Ag-Fe3O4G-C3N4Unmodified Ag-Fe is substantially better than to the degradation effect of octyl phenol3O4G-C3N4It is right
The degradation effect of octyl phenol, in 120min, has modified Ag-Fe3O4Class graphitic nitralloy carbon the degradation rate of octyl phenol is up to
97%；Refering to Fig. 4, with the extension of degradation time, octyl phenol solution absorbance is down to 0.003 by 0.102, according to absorbance with
The relation of octyl phenol solution concentration can calculate the change for learning octyl phenol solution concentration.
（4）Complete step（1）Arrive（3）For a degradation experiment, three degradation experiments are often carried out, one is reclaimed by strong magnet
Secondary photochemical catalyst, and the rate of recovery of survey calculation photochemical catalyst；The octyl phenol of the equal initial concentration all more renewed is tested every time
Solution.
Application of the novel magnetic multifunctional photocatalysis material in catalysis photocatalytic water prepares hydrogen, comprises the following steps：
（1）50mg photochemical catalysts are taken to add in the 100ml deionized waters containing volume fraction for 10% glycerine；
（2）Ultrasonic disperse 5min, it is in suspension system to make solution；
（3）It is furnished with visible ray filter plate in the daily lamp of 300W visible rays（The nm of Bo Chang≤400）The lower 1.5h of irradiation；
（4）By gas chromatographic measurement hydrogen output, single reading is recorded every 30min.
Embodiment 2
Novel magnetic multifunctional photocatalysis material is prepared, step is as follows：
S1. 3g melamines, 10ml HCl, 5ml glycerine, 2ml H are taken2O, is stirred after 10min at room temperature, and centrifugal filtration is dried.Will
Melamine by pretreatment is placed in porcelain crucible with cover, and 200 DEG C are heated in Muffle furnace（2 DEG C/min of heating rate）, then
It is heated to 500 DEG C（Heating rate is 5 DEG C/min）1h.After end, room temperature is naturally cooled to, faint yellow product g-C is collected3N4And
Grind into powder is stand-by；
S2. g-C made from 30mg steps S1 is taken3N4It is placed in 50ml deionized waters, ultrasonic oscillation 0.5h；
S3. 0.3g FeCl are continuously added2·4H2O, 20mg AgNO3With 0.1g PVP, stir after 2.5h, take 2ml mass concentrations
To be stirred vigorously 5min simultaneously in 27% ammonia solution addition mixed solution, make Fe (II) fully oxidized；
S4. suspension is transferred in the autoclave of 50ml teflon seals and heats 3.5h at 130 DEG C；
S5. question response terminates after cooling, takes out autoclave, products therefrom is washed 3 times with distilled water and absolute ethyl alcohol respectively
Afterwards, 13h is dried at 80 DEG C in an oven, obtain Ag-Fe3O4/g-C3N4 。
Application of the novel magnetic multifunctional photocatalysis material in degraded octyl phenol, comprises the following steps：
（1）In being the octyl group phenol solution that 20ppm volumes are 100ml by 50mg photochemical catalysts addition initial concentration；
（2）Using equipped with visible ray filter plate（The nm of Bo Chang≤400）10W daily LED as visible ray light source, mix
Magnetic agitation is carried out while closing liquid under visible light illumination, 1ml samples are taken out by centrifuging the remaining catalysis of removal every 30min
Agent obtains solution；
（3）Spectrophotometry instrument is used to survey its absorbance to detect the change of octyl phenol concentration；
（4）Complete step（1）Arrive（3）Operation be degradation experiment, often carry out three degradation experiments, reclaimed by strong magnet
Photochemical catalyst, and the rate of recovery of survey calculation photochemical catalyst；The octyl group of the equal initial concentration all more renewed is tested every time
Phenol solution.
Application of the novel magnetic multifunctional photocatalysis material in catalysis photocatalytic water prepares hydrogen, comprises the following steps：
（1）50mg photochemical catalysts are taken to add in the 100ml deionized waters containing volume fraction for 10% glycerine；
（2）Ultrasonic disperse 3min, it is in suspension system to make solution；
（3）It is furnished with visible ray filter plate in the daily lamp of 200W visible rays（The nm of Bo Chang≤400）The lower 3h of irradiation；
（4）By gas chromatographic measurement hydrogen output, single reading is recorded every 30min.
Embodiment 3
Novel magnetic multifunctional photocatalysis material is prepared, step is as follows：
S1. 5g melamines, 20ml HCl, 8ml glycerine, 5ml H are taken2O, is stirred after 30min at room temperature, and centrifugal filtration is dried.Will
Melamine by pretreatment is placed in porcelain crucible with cover, and 250 DEG C are heated in Muffle furnace（3 DEG C/min of heating rate）, then
It is heated to 520 DEG C（Heating rate is 10 DEG C/min）1h.After end, room temperature is naturally cooled to, faint yellow product g-C is collected3N4And
Grind into powder is stand-by；
S2. g-C made from 45mg steps S1 is taken3N4It is placed in 50ml deionized waters, ultrasonic oscillation 2h；
S3. 0.4g FeCl are continuously added2·4H2O, 30mg AgNO3With 0.2g PVP, after stirring 4h, the 3ml mass concentrations are taken to be
28% ammonia solution adds in mixed solution and is stirred vigorously 15min simultaneously, makes Fe (II) fully oxidized；
S4. suspension is transferred in the autoclave of 50ml teflon seals and heats 2.5h at 150 DEG C；
S5. question response terminates after cooling, takes out autoclave, products therefrom is washed 3 times with distilled water and absolute ethyl alcohol respectively
Afterwards, 12h is dried at 100 DEG C in an oven, obtain Ag-Fe3O4/g-C3N4 。
Application of the novel magnetic multifunctional photocatalysis material in degraded octyl phenol, comprises the following steps：
（1）In being the octyl group phenol solution that 20ppm volumes are 100ml by 50mg photochemical catalysts addition initial concentration；
（2）Using equipped with visible ray filter plate（The nm of Bo Chang≤400）30W daily LED as visible ray light source, mix
Magnetic agitation is carried out while closing liquid under visible light illumination, 1ml samples are taken out by centrifuging the remaining catalysis of removal every 30min
Agent obtains solution；
（3）Spectrophotometry instrument is used to survey its absorbance to detect the change of octyl phenol concentration；
（4）Complete step（1）Arrive（3）Operation be degradation experiment, often carry out three degradation experiments, reclaimed by strong magnet
Photochemical catalyst, and the rate of recovery of survey calculation photochemical catalyst；The octyl group of the equal initial concentration all more renewed is tested every time
Phenol solution.
Application of the novel magnetic multifunctional photocatalysis material in catalysis photocatalytic water prepares hydrogen, comprises the following steps：
（1）50mg photochemical catalysts are taken to add in the 100ml deionized waters containing volume fraction for 10% glycerine；
（2）Ultrasonic disperse 3min, it is in suspension system to make solution；
（3）It is furnished with visible ray filter plate in the daily lamp of 400W visible rays（The nm of Bo Chang≤400）The lower 1h of irradiation；
（4）By gas chromatographic measurement hydrogen output, single reading is recorded every 30min.
Described above is only the preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of novel magnetic multifunctional photocatalysis material, it is characterised in that：Comprise the following steps：
S1. appropriate melamine, HCl solution, glycerine, deionized water are taken, is mutually mixed and 10 ~ 30min is stirred at room temperature, from
Heart filtration drying；Melamine by pretreatment is placed in porcelain crucible with cover, heated in Muffle furnace, the temperature of Muffle furnace is first
200 ~ 250 DEG C are warming up to 2 ~ 4 DEG C/min speed, then 500 ~ 550 DEG C, keeping temperature are warming up to 5 ~ 10 DEG C/min speed
Heat 1 ~ 3h；After heating terminates, room temperature is naturally cooled to, faint yellow product g-C is collected3N4And grind into powder is stand-by；
S2. g-C made from appropriate step S1 is taken3N4It is scattered in 50ml deionized waters, 0.5 ~ 2h of ultrasonic oscillation；
S3. appropriate FeCl is added in the aqueous solution in step s 22·4H2O, AgNO3With PVP（Polyvinylpyrrolidone）, stir
Mix after 2.5 ~ 4h, take appropriate ammonia solution to add in foregoing mixed solution, while being stirred vigorously 5 ~ 15min, make Fe (II) fully oxygen
Change；
S4. the obtained suspension of step S3 is transferred in the autoclave of 50ml teflon seals and added at 130 ~ 150 DEG C
2.5 ~ 3.5h of heat；
S5. after question response terminates and cooled down, autoclave is taken out, products therefrom is washed 3 times with distilled water and absolute ethyl alcohol respectively
Afterwards, 12 ~ 13h is dried at 80 ~ 100 DEG C of baking oven, product Ag-Fe is obtained3O4/g-C3N4 。
2. a kind of preparation method of novel magnetic multifunctional photocatalysis material according to claim 1, it is characterised in that：Institute
State melamine in step S1,35% HCl solution, glycerine and H2O specifically used amount is：3~5g melamines, 10 ~ 20ml HCl, 5 ~
10ml glycerine, 2 ~ 5ml H2O。
3. a kind of preparation method of novel magnetic multifunctional photocatalysis material according to claim 1, it is characterised in that：Institute
State the FeCl in step S32·4H2O, AgNO3With PVP（Polyvinylpyrrolidone）Specific addition be：0.3g~0.6g
FeCl2·4H2O, 20~35mg AgNO3, 0.1~0.2g PVP（Polyvinylpyrrolidone）.
4. a kind of preparation method of novel magnetic multifunctional photocatalysis material according to claim 1, it is characterised in that：Institute
The mass concentration for stating ammonia solution in step S3 is 25 ~ 28%, and addition is 2 ~ 3.5ml.
5. a kind of novel magnetic multifunctional photocatalysis material, multi-functional using the novel magnetic described in any one of claim 1 ~ 4
The preparation method of catalysis material is made.
6. a kind of application of novel magnetic multifunctional photocatalysis material, wherein novel magnetic multifunctional photocatalysis material uses right
It is required that the preparation method of the novel magnetic multifunctional photocatalysis material described in 1 ~ 4 any one is made, it is characterised in that：The application
Including catalysis material the application of application and catalysis material in catalysis photocatalytic water prepares hydrogen in degraded octyl phenol.
7. the application of novel magnetic multifunctional photocatalysis material according to claim 6, it is characterised in that：The photocatalysis
Application of the material in degraded octyl phenol comprises the following steps：
（1）By 50mg photochemical catalysts Ag-Fe3O4/g-C3N4It is the octyl group phenol solution that 20ppm, volume are 100ml to add initial concentration
In, form mixing suspension；
（2）Foregoing mixing suspension under visible light illumination while carry out magnetic agitation, every 30min take out 1ml samples, lead to
Cross catalyst remaining in centrifugally operated removal sample and obtain solution；
（3）Spectrophotometry instrument is used to detect the absorbance of sample solution to calculate octyl phenol concentration；
（4）Complete step（1）Arrive（3）Operation be degradation experiment, often carry out three degradation experiments, reclaimed by strong magnet
Photochemical catalyst, and the rate of recovery of survey calculation photochemical catalyst；The octyl group of the equal initial concentration all more renewed is tested every time
Phenol solution.
8. the application of novel magnetic multifunctional photocatalysis material according to claim 7, it is characterised in that：Step（2）In
Visible ray light source be equipped with visible ray filter plate（The nm of Bo Chang≤400）10~30 W daily LED.
9. the application of novel magnetic multifunctional photocatalysis material according to claim 6, it is characterised in that：The photocatalysis
Application of the material in catalysis photocatalytic water prepares hydrogen comprises the following steps：
（1）Take 50mg photochemical catalysts Ag-Fe3O4/g-C3N4Add in 100ml deionized waters, 10% body is contained in the deionized water
The glycerine of fraction；
（2）3 ~ 5min of ultrasonic disperse, it is in suspension system to make solution；
（3）1 ~ 3h is irradiated under visible light, and the light source of the visible ray is equipped with visible ray filter plate（The nm of Bo Chang≤400）'s
200 ~ 400W day lamps；
（4）By gas chromatographic measurement hydrogen output, a data are recorded every 30min.
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| CN108306001A (en) * | 2018-01-08 | 2018-07-20 | 北京科技大学 | Lithium ion battery negative material Fe3O4The preparation method of/N-C |
| CN108380247A (en) * | 2018-03-20 | 2018-08-10 | 河南大学 | Fe3O4-NH2The preparation method and applications of@AgNPs composite materials |
| CN109465037A (en) * | 2018-11-30 | 2019-03-15 | 华南理工大学 | The magnetic CDs-MoS of micropollutants in a kind of degradation water2-Fe3O4The green synthesis method of catalysis material |
| CN113926483A (en) * | 2021-11-22 | 2022-01-14 | 西南林业大学 | Magnetic recovery type double-Fenton Fe3O4Preparation method and application of (E) -Fe-CN composite material |
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| CN113926483A (en) * | 2021-11-22 | 2022-01-14 | 西南林业大学 | Magnetic recovery type double-Fenton Fe3O4Preparation method and application of (E) -Fe-CN composite material |
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