CN107649162A - A kind of composite photo-catalyst and preparation method and application - Google Patents
A kind of composite photo-catalyst and preparation method and application Download PDFInfo
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- CN107649162A CN107649162A CN201710948003.1A CN201710948003A CN107649162A CN 107649162 A CN107649162 A CN 107649162A CN 201710948003 A CN201710948003 A CN 201710948003A CN 107649162 A CN107649162 A CN 107649162A
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- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 33
- YCIHPQHVWDULOY-FMZCEJRJSA-N (4s,4as,5as,6s,12ar)-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O YCIHPQHVWDULOY-FMZCEJRJSA-N 0.000 claims abstract description 15
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 13
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 8
- 239000001632 sodium acetate Substances 0.000 claims abstract description 8
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 7
- 231100000719 pollutant Toxicity 0.000 claims abstract description 7
- 230000000593 degrading effect Effects 0.000 claims abstract description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 95
- 239000003054 catalyst Substances 0.000 claims description 43
- 239000002077 nanosphere Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 15
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 230000004048 modification Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 230000003115 biocidal effect Effects 0.000 description 7
- 229920000877 Melamine resin Polymers 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 235000011091 sodium acetates Nutrition 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004098 Tetracycline Substances 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 235000012149 noodles Nutrition 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229960002180 tetracycline Drugs 0.000 description 2
- 229930101283 tetracycline Natural products 0.000 description 2
- 235000019364 tetracycline Nutrition 0.000 description 2
- 150000003522 tetracyclines Chemical class 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 231100000463 ecotoxicology Toxicity 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 210000003754 fetus Anatomy 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
-
- 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
-
- 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
- B01J37/088—Decomposition of a metal salt
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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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to catalysis material synthesis technical field.A kind of composite photo-catalyst and preparation method and application are refered in particular to, available for quadracycline pollutant of degrading under visible light.Precise Iron(III) chloride hexahydrate is dissolved in stirring in ethylene glycol and obtains solution A.Sodium acetate is added in solution A and forms solution B.G C are added in solution B3N4, stir and form solution C.Solution C is transferred in reactor, reacts 6h in 200 DEG C of baking oven.After room temperature, centrifuge, wash, be dried to obtain sample.
Description
Technical field
The invention belongs to catalysis material synthesis technical field, using simple and quick solvent-thermal method one-step synthesis by Fe3O4
Nanosphere modifies g-C3N4Fe3O4/g-C3N4Composite mesoporous photochemical catalyst, it is dirty available for quadracycline of degrading under visible light
Contaminate thing.
Background technology
China is antibiotic usage and big producer, produces the outlet of antibiotic raw material sub-fraction per year, and remaining is largely personal
(including medical treatment and agricultural use), annual consumption 138g or so per capita, and U.S. annual consumption only 13g per capita according to statistics.According to
2006~2007 annual Ministry of Public Health whole nation Bacterial resistance surveillance results show that national hospital's antibacterials year utilization rate is up to
74%, and in developed countries such as the U.S. and Britains, the antibiotic utilization rate of hospital is only 22%~25%.In the inpatient of China, resist
The utilization rate of raw element is then up to 70%, wherein surgical patients almost everybody use antibiotic, ratio is up to 97%.These digital tables
Bright China has become one of country of abuse of antibiotics problem most serious in the world.Antibiotic is originally to be used to treat various non-diseases
The medicine of poison infection, but shown many side effects in Clinical practice, research shows that part antibiotic has to fetus
Teratogenesis.Tetracycline medication is clinically to use most, most widely used a kind of antibiotic, due to its have it is water-soluble compared with
The features such as largely discharging with original shape after good, metabolism in vivo and be not susceptible to biodegradation in the environment, so as to easily in water
Storage and accumulation form Environmental Residues thing in environment, cause a series of ecological pollution and influence human health problems.Meanwhile by
Wider in such medicine antibacterial spectrum, its caused eco-toxicology effects is very huge, therefore, effectively removes hydrochloric acid in environment
Tetracycline residue thing is very urgent.Research find the treatment technology conventional with some such as adsorb, be electrolysed, microbial degradation phase
Than, Photocatalyst has using renewable solar energy, environment-friendly, pollutant removal is thorough, cost is cheap etc. significantly
Advantage.
The core of Photocatalyst is the efficient conductor photocatalysis material of exploitation.Recent study is more partly to be led
Body photochemical catalyst TiO2, because it is wide band gap semiconducter, ultraviolet can only be absorbed, causes sun light utilization efficiency very low.Although also
Develop substantial amounts of TiO2Based composites, but the quick compound potential application for still limiting them of electron-hole pair.Graphite
Phase carbon nitride (g-C3N4) it is a kind of novel semi-conductor catalysis material favored very much, not only there is narrower energy gap
(2.7eV) can responding to visible light, but also there is acid and alkali resistance, photoetch and environmental protection.However, g-C3N4Still have
In place of some shortcomings, such as specific surface area is relatively low, photo-generate electron-hole is higher to recombination rate, so as to cause its photocatalysis performance
It is relatively low.
During people explore novel photocatalyst, Fe is found3O4It is a kind of potential catalysis material.Fe3O4It is
By Fe2+、Fe3+And O2-The inverse spinel crystal structure of composition, allow its electronics in Fe2+And Fe3+Between transmitted, so as to
With special electromagnetic property.Fe3O4Possess high saturation magnetization, Curie temperature and electric conductivity, while also have well
Weatherability, light resistance, ultraviolet radiation absorption and shielding character, in microwave absorbing material, catalyst carrier, magnetic recording material, electronics
Material and bio-medical material etc. have a wide range of applications, so to Fe3O4Controlledly synthesis and its physical and chemical performance
Study significant.The iron oxide of nanoscale due to the quantum size effect of nano material, surface and interface effect etc.,
And with the physical and chemical properties different from body material.By Fe3O4For the composite photocatalyst material of composite construction cell formation,
Such as metal/Fe3O4, graphene/Fe3O4、WO3/Fe3O4、TiO2/Fe3O4Etc. showing unique, efficient photocatalysis performance, but this
It can not but be realized in one-component catalyst.It is different from other most metals oxide semiconductors, nanometer Fe3O4Have
(electrical conductivity is up to 1.9 × 10 to good electric conductivity6S m-1) and band structure matching, it can be good at and g-C3N4Carry out coupling
Close, and photocatalysis performance is improved by strengthening separation and the transfer of electron-hole pair, compensate for single g-C3N4Photoproduction electricity
The shortcomings that son-hole is higher to recombination rate.Therefore, by nanometer Fe3O4To g-C3N4Nanometer sheet carries out surface modification, can prepare
Efficient visible light composite photocatalyst.
In this work, by simple and quick solvent-thermal method one-step synthesis by Fe3O4Nanosphere surface modification g-C3N4's
Fe3O4/g-C3N4Composite mesoporous photochemical catalyst, for photocatalytic degradation quadracycline.With g-C3N4Compare, optimal Fe3O4/g-
C3N4Composite photo-catalyst is in 120min to the degradation rate of quadracycline up to 70.9%, about g-C3N4(23.3%)
3.04 again.Fe3O4Nanosphere is to g-C3N4Surface modification effect significantly improve its capacity gauge and current-carrying to solar spectrum
The separative efficiency of son, while specific surface area and surface-active site are added, finally substantially increase and quadracycline is polluted
The degradation capability of thing.Up to the present, not yet find using a simple and quick step solvent-thermal method in g-C3N4Surface modification
Fe3O4Nanosphere builds Fe3O4/g-C3N4Composite mesoporous photochemical catalyst.
The content of the invention
The invention belongs to nano material synthesis technical field, using simple and quick solvent-thermal method one-step synthesis by Fe3O4Receive
Rice ball modification g-C3N4Fe3O4/g-C3N4Composite mesoporous photochemical catalyst, available for Visible Light Induced Photocatalytic quadracycline pollutant.
The preparation method characteristic of the present invention comprises the following steps：
One, prepares g-C3N4Photochemical catalyst
1. melamine is taken to be put into open pot, with 2 DEG C of min-1Heating rate, be heated to 550 DEG C from room temperature, keep
4h。
2. taking out yellow solid after being cooled to room temperature, powder is ground to agate mortar, obtains g-C3N4Photochemical catalyst.
Two, prepare Fe3O4/g-C3N4Composite mesoporous photochemical catalyst
1. precise Iron(III) chloride hexahydrate is dissolved in stirring in ethylene glycol and obtains solution A.
2. sodium acetate is added in solution A forms solution B.
3. g-C is added in solution B3N4, stir and form solution C.
4. solution C is transferred in reactor, 6h is reacted in 200 DEG C of baking oven.
5. after room temperature, centrifuge, wash, be dried to obtain sample.
The mass volume ratio of sodium acetate and ethylene glycol is 3.6g：35mL.
Sodium acetate and g-C3N4Mass volume ratio be 36:5.
Wherein the amount of Iron(III) chloride hexahydrate is according to Fe3O4And g-C3N4Mass ratio be 0.05：0.5 to 0.15：0.5, most
Fe is prepared into eventually3O4To g-C3N4Mass percent be respectively 10wt% to 30wt% Fe3O4/g-C3N4Composite mesoporous light is urged
Agent；It is preferred that 20%.
In step (3), the time of magnetic agitation is 12h.
Drying temperature is 60 DEG C in step (5), drying time 12h.
In this work, X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), transmission electron microscope are utilized
(TEM)、N2The means such as adsorption-desorption isothermal and BJH pore-size distributions are to Fe3O4/g-C3N4Composite mesoporous photochemical catalyst carries out table
Sign.Fig. 1 is g-C3N and Fe3O4/g-C3N4The XRD of composite mesoporous photochemical catalyst.Through Fe3O4After nanosphere modification, g- is found
C3N4Stronger diffraction maximum positioned at 2 θ=27.6 ° decreases, and this is probably due to Fe3O4Nanosphere is modified in g-C3N4Surface institute
Cause.Meanwhile positioned at 2 θ be 35.4 ° and 62.6 ° at occur coming from Fe3O4Diffraction maximum, this shows Fe3O4Success is modified in g-
C3N4Surface.Fig. 2 (a) and (e) are g-C respectively3N4FESEM and TEM photos, it is observed that g-C3N4Structure in the form of sheets.Fig. 2
(b) and (c) in Fe3O4FESEM photos show obtain Fe3O4For uniform nanometer spherical.Fig. 2 (d) and (f) are Fe respectively3O4/
g-C3N4FESEM the and TEM photos of composite mesoporous photochemical catalyst, it is evident that Fe3O4Nanosphere is dispersed in g-C3N4Lamella knot
Structure surface, Fe in Fig. 2 (g)3O4/g-C3N4First vegetarian noodles of composite mesoporous photochemical catalyst sweeps photo and shows that each element is uniformly distributed.Separately
Outside, the N in Fig. 3 (a, b)2Adsorption-desorption curve and pore-size distribution show that two kinds of samples are meso-hole structure, its 25nm or so
Pore-size distribution is g-C3N4Meso-hole structure, and Fe3O4/g-C3N4Pore-size distribution of the composite mesoporous photochemical catalyst in 5nm or so can
Fe can be come from3O4Microballoon.Kinetic curve in Fig. 4 (a, b) shows the Fe obtained3O4/g-C3N4Composite mesoporous photocatalysis
Agent significantly enhances the photocatalysis performance of degraded quadracycline pollutant, while has higher stability and reusable
Property.
In the present invention, by the amount controllable preparation Fe for being accurately controlled reaction condition and reactant3O4/g-C3N4It is mesoporous
Composite photo-catalyst.g-C3N4By Fe3O4Significantly improved after nanosphere surface modification to the absorbability of light and carrier
Separative efficiency, specific surface area and surface-active site are added, be advantageous to improve photocatalytic activity.The present invention is different from existing skill
The distinguishing feature of art is by Fe using this simple and quick solvent-thermal method one-step synthesis3O4Nanosphere surface modification g-
C3N4Fe3O4/g-C3N4Composite mesoporous photochemical catalyst, solve some photochemical catalysts under visible light and quadracycline is polluted
The problem of thing degradation efficiency is low.
The main object of the present invention：First, it is that accuracy controlling reaction condition and reactant are passed through using simple solvent-thermal method
Amount synthesize by Fe3O4Nanosphere surface modification g-C3N4Fe3O4/g-C3N4Composite mesoporous photochemical catalyst provides one typically
Example；2nd, Fe3O4/g-C3N4Composite mesoporous photochemical catalyst can be used for photocatalytic degradation quadracycline pollutant under visible ray.
Beneficial effect
Using simple and quick solvent-thermal method one-step synthesis by Fe3O4Nanosphere surface modification g-C3N4Fe3O4/g-C3N4
Composite mesoporous photochemical catalyst, its quadracycline of degrading under visible light illumination show excellent photocatalytic activity；The present invention
Technique is very simple, the reaction time is shorter, so as to reduce energy consumption and reaction cost, is easy to produce in batches, nontoxic, meets
Environment-friendly requirement.
Brief description of the drawings
Fig. 1 g-C3N4And Fe3O4/g-C3N4The XRD spectrums of composite mesoporous photochemical catalyst.
Fig. 2 g-C3N4FESEM (a) and TEM (e) photos, Fe3O4(b, c) and Fe3O4/g-C3N4Composite mesoporous photocatalysis
The FESEM photos of agent (d), Fe3O4/g-C3N4The first vegetarian noodles of TEM (f) of composite mesoporous photochemical catalyst sweeps (g) photo.
Fig. 3 g-C3N4And Fe3O4/g-C3N4The N of composite mesoporous photochemical catalyst2Adsorption-desorption isothermal (a) and aperture point
Cloth (b) figure.
Sample to the degradation kinetics curve (a) of quadracycline and circulates the degradation rate (b) of five times under Fig. 4 visible rays
Figure.
Embodiment
Embodiment 1：10wt%Fe3O4/g-C3N4The preparation of composite mesoporous photochemical catalyst
One, prepares g-C3N4Photochemical catalyst
1. melamine is taken to be put into open pot, with 2 DEG C of min-1Heating rate, be heated to 550 DEG C from room temperature, keep
4h。
2. taking out yellow solid after being cooled to room temperature, powder is ground to agate mortar, obtains mesoporous g-C3N4Photocatalysis
Agent.
Two, prepare 10wt%Fe3O4/g-C3N4Composite mesoporous photochemical catalyst
Solution A is obtained 1. weighing 0.1750g Iron(III) chloride hexahydrates and being dissolved in stirring in 35mL ethylene glycol.
2. 3.6g sodium acetates are added in solution A forms solution B.
3. 0.5g g-C is added in solution B3N4, magnetic agitation 12h formation solution Cs.
4. solution C is transferred in reactor, 6h is reacted in 200 DEG C of baking oven.
5. after room temperature, centrifugation, washing, dry 12h obtains sample in 60 DEG C of baking oven.
Embodiment 2：15wt%Fe3O4/g-C3N4The preparation of composite mesoporous photochemical catalyst
One, prepares g-C3N4Photochemical catalyst
1. melamine is taken to be put into open pot, with 2 DEG C of min-1Heating rate, be heated to 550 DEG C from room temperature, keep
4h。
2. taking out yellow solid after being cooled to room temperature, powder is ground to agate mortar, obtains mesoporous g-C3N4Photocatalysis
Agent.
Two, prepare 15wt%Fe3O4/g-C3N4Composite mesoporous photochemical catalyst
Solution A is obtained 1. weighing 0.2625g Iron(III) chloride hexahydrates and being dissolved in stirring in 35mL ethylene glycol.
2. 3.6g sodium acetates are added in solution A forms solution B.
3. 0.5g g-C is added in solution B3N4, magnetic agitation 12h formation solution Cs.
4. solution C is transferred in reactor, 6h is reacted in 200 DEG C of baking oven.
5. after room temperature, centrifugation, washing, dry 12h obtains sample in 60 DEG C of baking oven.
Embodiment 3：20wt%Fe3O4/g-C3N4Composite mesoporous photochemical catalyst
One, prepares g-C3N4Photochemical catalyst
1. melamine is taken to be put into open pot, with 2 DEG C of min-1Heating rate, be heated to 550 DEG C from room temperature, keep
4h。
2. taking out yellow solid after being cooled to room temperature, powder is ground to agate mortar, obtains mesoporous g-C3N4Photocatalysis
Agent.
Two, prepare 20wt%Fe3O4/g-C3N4Composite mesoporous photochemical catalyst
Solution A is obtained 1. weighing 0.3501g Iron(III) chloride hexahydrates and being dissolved in stirring in 35mL ethylene glycol.
2. 3.6g sodium acetates are added in solution A forms solution B.
3. 0.5g g-C is added in solution B3N4, magnetic agitation 12h formation solution Cs.
4. solution C is transferred in reactor, 6h is reacted in 200 DEG C of baking oven.
5. after room temperature, centrifugation, washing, dry 12h obtains sample in 60 DEG C of baking oven.
Embodiment 4：25wt%Fe3O4/g-C3N4Composite mesoporous photochemical catalyst
One, prepares g-C3N4Photochemical catalyst
1. melamine is taken to be put into open pot, with 2 DEG C of min-1Heating rate, be heated to 550 DEG C from room temperature, keep
4h。
2. taking out yellow solid after being cooled to room temperature, powder is ground to agate mortar, obtains mesoporous g-C3N4Photocatalysis
Agent.
Two, prepare 25wt%Fe3O4/g-C3N4Composite mesoporous photochemical catalyst
Solution A is obtained 1. weighing 0.4376g Iron(III) chloride hexahydrates and being dissolved in stirring in 35mL ethylene glycol.
2. 3.6g sodium acetates are added in solution A forms solution B.
3. 0.5g g-C is added in solution B3N4, magnetic agitation 12h formation solution Cs.
4. solution C is transferred in reactor, 6h is reacted in 200 DEG C of baking oven.
5. after room temperature, centrifugation, washing, dry 12h obtains sample in 60 DEG C of baking oven.
Embodiment 5：30wt%Fe3O4/g-C3N4The preparation of composite mesoporous photochemical catalyst
One, prepares g-C3N4Photochemical catalyst
1. melamine is taken to be put into open pot, with 2 DEG C of min-1Heating rate, be heated to 550 DEG C from room temperature, keep
4h。
2. taking out yellow solid after being cooled to room temperature, powder is ground to agate mortar, obtains mesoporous g-C3N4Photocatalysis
Agent.
Two, prepare 30wt%Fe3O4/g-C3N4Composite mesoporous photochemical catalyst
Solution A is obtained 1. weighing 0.5251g Iron(III) chloride hexahydrates and being dissolved in stirring in 35mL ethylene glycol.
2. 3.6g sodium acetates are added in solution A forms solution B.
3. 0.5g g-C is added in solution B3N4, magnetic agitation 12h formation solution Cs.
4. solution C is transferred in reactor, 6h is reacted in 200 DEG C of baking oven.
5. after room temperature, centrifugation, washing, dry 12h obtains sample in 60 DEG C of baking oven.
By strictly regulating and controlling the amount of Iron(III) chloride hexahydrate, ethylene glycol, sodium acetate, with simple and quick solvent-thermal method one
Step synthesis is by Fe3O4Nanosphere modifies g-C3N4Fe3O4/g-C3N4Composite mesoporous photochemical catalyst, 50mg each sample has been investigated respectively
Under visible light to quadracycline solution (10mg/L) degradation effect, this Fe is as a result shown3O4/g-C3N4It is composite mesoporous
Photochemical catalyst significantly enhances photocatalytic activity.In addition, 20wt% Fe3O4/g-C3N4Composite mesoporous photochemical catalyst has most
Good catalytic performance, reacted by 120min visible light catalytic, the degradation rate of quadracycline reaches 70.9%, shows to be obtained
This Fe obtained3O4/g-C3N4Composite mesoporous photochemical catalyst can be applied to the improvement of quadracycline pollutant.
Claims (7)
1. a kind of composite photo-catalyst, the composite photo-catalyst is Fe3O4Nanosphere modifies g-C3N4Fe3O4/g-C3N4It is mesoporous
Composite photo-catalyst, it is characterised in that prepare with the following method：
(1) precise Iron(III) chloride hexahydrate is dissolved in stirring in ethylene glycol and obtains solution A；
(2) sodium acetate is added in solution A and forms solution B；
(3) g-C is added in solution B3N4, stir and form solution C；
(4) solution C is transferred in reactor, reacts 6h in 200 DEG C of baking oven；
(5) after after naturally cool to room temperature, centrifuge, wash, be dried to obtain sample.
A kind of 2. composite photo-catalyst as claimed in claim 1, it is characterised in that the mass volume ratio of sodium acetate and ethylene glycol
For 3.6g：35mL；Sodium acetate and g-C3N4Mass volume ratio be 36:5.
3. a kind of composite photo-catalyst as claimed in claim 1, it is characterised in that the amount of Iron(III) chloride hexahydrate is according to Fe3O4
And g-C3N4Mass ratio be 0.05：0.5 to 0.15：0.5, finally it is prepared into Fe3O4To g-C3N4Mass percent be
10wt% to 30wt% Fe3O4/g-C3N4Composite mesoporous photochemical catalyst.
A kind of 4. composite photo-catalyst as claimed in claim 3, it is characterised in that Fe3O4To g-C3N4Mass percent be
20wt%.
5. a kind of composite photo-catalyst as claimed in claim 1, it is characterised in that in step (3), the time of magnetic agitation is
12h。
6. a kind of composite photo-catalyst as claimed in claim 1, it is characterised in that drying temperature is 60 DEG C in step (5), is done
The dry time is 12h.
7. the purposes of the composite photo-catalyst as described in claim 1-6 is any, for quadracycline of degrading under visible light
Pollutant.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109174154A (en) * | 2018-09-13 | 2019-01-11 | 浙江大学 | The application of antibiotic in a kind of doping modification method and degrading waste water of nitrogen carbide |
| CN109647486A (en) * | 2019-01-28 | 2019-04-19 | 华东交通大学 | Ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst preparation method and application |
| CN109847783A (en) * | 2019-01-30 | 2019-06-07 | 太原理工大学 | A kind of Fe3+/CdIn2S4/g-C3N4The preparation method and applications of ternary light fenton catalyst |
| CN112044460A (en) * | 2020-08-05 | 2020-12-08 | 太原理工大学 | Method for enhancing mineralization of tetracycline antibiotics by graphite-phase carbon nitride |
| CN112934249A (en) * | 2021-03-08 | 2021-06-11 | 西北师范大学 | Preparation and application of phosphorus-doped graphite carbon nitride/ferroferric oxide composite material |
| CN113856729A (en) * | 2021-11-04 | 2021-12-31 | 齐鲁工业大学 | Photodegradation catalyst, preparation method thereof and application thereof in degrading antibiotics |
| CN114029080A (en) * | 2021-12-17 | 2022-02-11 | 江苏科技大学 | Ternary heterojunction visible-light-driven photocatalyst and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109174154A (en) * | 2018-09-13 | 2019-01-11 | 浙江大学 | The application of antibiotic in a kind of doping modification method and degrading waste water of nitrogen carbide |
| CN109647486A (en) * | 2019-01-28 | 2019-04-19 | 华东交通大学 | Ferroso-ferric oxide-graphite-like carbonitride composite magnetic photochemical catalyst preparation method and application |
| CN109847783A (en) * | 2019-01-30 | 2019-06-07 | 太原理工大学 | A kind of Fe3+/CdIn2S4/g-C3N4The preparation method and applications of ternary light fenton catalyst |
| CN109847783B (en) * | 2019-01-30 | 2022-03-04 | 太原理工大学 | Fe3+/CdIn2S4/g-C3N4Preparation method and application of ternary photo-Fenton catalyst |
| CN112044460A (en) * | 2020-08-05 | 2020-12-08 | 太原理工大学 | Method for enhancing mineralization of tetracycline antibiotics by graphite-phase carbon nitride |
| CN112044460B (en) * | 2020-08-05 | 2022-11-08 | 太原理工大学 | Method for enhancing graphite-phase carbon nitride mineralization tetracycline antibiotics |
| CN112934249A (en) * | 2021-03-08 | 2021-06-11 | 西北师范大学 | Preparation and application of phosphorus-doped graphite carbon nitride/ferroferric oxide composite material |
| CN112934249B (en) * | 2021-03-08 | 2023-01-10 | 西北师范大学 | Preparation and application of phosphorus-doped graphite carbon nitride/ferroferric oxide composite material |
| CN113856729A (en) * | 2021-11-04 | 2021-12-31 | 齐鲁工业大学 | Photodegradation catalyst, preparation method thereof and application thereof in degrading antibiotics |
| CN114029080A (en) * | 2021-12-17 | 2022-02-11 | 江苏科技大学 | Ternary heterojunction visible-light-driven photocatalyst and preparation method thereof |
| CN114029080B (en) * | 2021-12-17 | 2024-02-27 | 江苏科技大学 | Ternary heterojunction visible light catalyst and preparation method thereof |
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