CN110180540A - Ag dopen Nano metal oxide composite and its application in photocatalytic degradation tetracycline - Google Patents
Ag dopen Nano metal oxide composite and its application in photocatalytic degradation tetracycline Download PDFInfo
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- CN110180540A CN110180540A CN201910364433.8A CN201910364433A CN110180540A CN 110180540 A CN110180540 A CN 110180540A CN 201910364433 A CN201910364433 A CN 201910364433A CN 110180540 A CN110180540 A CN 110180540A
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- 239000002131 composite material Substances 0.000 title claims abstract description 74
- 239000004098 Tetracycline Substances 0.000 title claims abstract description 44
- 229960002180 tetracycline Drugs 0.000 title claims abstract description 44
- 229930101283 tetracycline Natural products 0.000 title claims abstract description 44
- 235000019364 tetracycline Nutrition 0.000 title claims abstract description 44
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 42
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 40
- 150000003522 tetracyclines Chemical class 0.000 title claims abstract description 37
- 238000013033 photocatalytic degradation reaction Methods 0.000 title abstract description 7
- 230000015556 catabolic process Effects 0.000 claims abstract description 29
- 238000006731 degradation reaction Methods 0.000 claims abstract description 29
- 239000012876 carrier material Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 18
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 239000004332 silver Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims description 29
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 24
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 21
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 20
- 150000004693 imidazolium salts Chemical class 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 19
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 150000002460 imidazoles Chemical class 0.000 claims description 14
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000002023 wood Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- 238000005286 illumination Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 150000003851 azoles Chemical class 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000003837 high-temperature calcination Methods 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 3
- 239000010457 zeolite Substances 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 23
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 11
- 239000002105 nanoparticle Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound 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)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 7
- 230000003115 biocidal effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- -1 zeolite imidazole ester Chemical class 0.000 description 2
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 201000006549 dyspepsia Diseases 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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)
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a kind of Ag dopen Nano metal oxide composite and its applications in photocatalytic degradation tetracycline；First synthetic zeolite imidazate frame structure material, then in its surface doping Nano silver grain, obtained solid is restored at high temperature, obtains Ag doped with nano metal oxide composite.The present invention constructs a series of carrier materials, method by introducing silver and high-temperature calcination, six kinds of different composite materials are synthesized, wherein, use the tetracycline of 50mg Ag@ZnO (8) or Ag@ZnO (90) degradation 100ml 10mg/L, dark absorption is placed under simulated solar radiant for 30 minutes carries out photocatalytic degradation, solution concentration can be reduced to 16.4% of concentration at the end of dark reaction after 120 minutes, photocatalytic activity is up to 83.6%, illustrate that its disposal efficiency is efficient, it is reused many times by recycling, it was demonstrated that its repeatability.
Description
Technical field
The present invention relates to nanocomposite technical fields, and in particular to a kind of nano metal oxygen for adulterating Nano silver grain
The preparation method of compound composite material and its application in photocatalytic degradation tetracycline.
Background technique
As antibiotic is widely used as animal drug and feed addictive in recent years, environmental pollution is caused.Past is several
Nian Lai detects antibiotic and its metabolin in surface water, underground water and drinking water.Drawn by various sources into environment
Entering antibiotic residue will lead to serious environmental problem, including ecological disruption and human health damage.Present in water and soil
Antibiotic will lead to some allergy and toxicity.The removal or degradation of drug contamination object have become an important research topic.
Tetracycline (TC) indigestion in animal alimentary canal, 50-80% are discharged by excrement and urine.People are increasingly
Worry that the TC being rich in using animal fertilizer as plant nutrient source can generate potential impact to underground water or soil.In addition, TC exists
Quite lasting in soil, and by fertilising repeatedly accumulation, damaged ecological environment, the body that compromises the mankind it is strong
Health.Due to its antibiotic property, the waters of TC residual or pollution cannot effectively be eliminated by traditional biological method.Therefore processing Fourth Ring
Pollution caused by element is extremely urgent, and carries out photochemical catalytic oxidation to it using the metal oxide composite of nanoparticle doped
It is the processing method of a kind of promising and widely used removal water pollutant.
Nano silver grain stability with higher and catalytic activity, but in practical applications, Nano silver grain is used as and urges
Agent needs a good carrier.In previous document report, common carrier is mainly TiO2、CeO2Deng, but it is negative
The Nano silver grain size being downloaded on oxide is uncontrollable, and is distributed nor too uniformly, it is therefore desirable to find one more preferably
Carrier adulterate Nano silver grain.
Summary of the invention
The object of the present invention is to provide a kind of preparation sides of nano metal oxide composite material for adulterating Nano silver grain
Nano silver grain is loaded to nano-metal-oxide surface using the method for in-situ reducing by method, to realize that efficient degradation is water-soluble
Tetracycline in liquid.
The uniform preparation process for loading to catalyst surface of Nano silver grain is relative complex, be the problem that faces at present it
One.The present invention constructs a series of ZIFs materials, the method by introducing silver and high-temperature calcination, synthesized six kinds it is different compound
Material, these materials are used equally for the catalytic degradation of tetracycline aqueous solution under visible light.
The present invention uses following specific technical solution:
A kind of Ag dopen Nano metal oxide composite, the preparation side of the Ag dopen Nano metal oxide composite
Method the following steps are included:
(1) salt is mixed with imidazolium compounds solution, reaction obtains carrier material；Salt is Zn(NO3)2·6H2O or Co
(NO3)2·6H2O；The imidazolium compounds is 2-methylimidazole or imidazoles -2- formaldehyde；
(2) carrier material is dispersed in silver nitrate solution, stir process, then filters, is dry, obtains silver-colored carrier composite wood
Material；
(3) obtained silver-colored carrier composite material is obtained into Ag dopen Nano metal oxide composite by high temperature reduction.
In step (1), when salt is Zn(NO3)2·6H2O, when imidazolium compounds is 2-methylimidazole, Zn(NO3)2·6H2O、
The mass ratio of 2-methylimidazole is (1~2): (3~4), and the temperature of reaction is room temperature, and the time is 12 hours；When salt is Zn
(NO3)2·6H2O, imidazolium compounds is imidazoles -2- formaldehyde, Zn(NO3)2·6H2O, the mass ratio of imidazoles -2- formaldehyde is (6~7)
: (2~3), the temperature of reaction are room temperatures, and the time is 10 hours；When salt is Co(NO3)2·6H2O, imidazolium compounds is 2- methyl
When imidazoles, Co(NO3)2·6H2O, the mass ratio of 2-methylimidazole is (1~2): (9~10), the temperature of reaction are room temperature, time
It is 24 hours.
Specifically, Ag dopen Nano metal oxide composite of the invention is prepared by following methods:
A kind of preparation method of Ag@ZnO (8) composite material, comprising the following steps:
(1) by Zn(NO3)2·6H2O is mixed with the methanol solution of 2-methylimidazole, and reaction obtains Z8 carrier material；
(2) Z8 carrier material being dispersed in silver nitrate solution, then stir process filters, and it is dry, obtain Ag@Z8 intermediate；
(3) obtained Ag@Z8 intermediate is obtained into Ag@ZnO (8) composite material, i.e. Ag dopen Nano metal by high temperature reduction
Oxide composite.
A kind of Ag@Co2O3The preparation method of composite material, comprising the following steps:
(1) by Co(NO3)2·6H2O is mixed with the methanol solution of 2-methylimidazole, and reaction obtains Z6 carrier material；
(2) Z6 carrier material being dispersed in silver nitrate solution, then stir process filters, and it is dry, obtain Ag@Z6 intermediate；
(3) obtained Ag@Z6 intermediate is obtained into Ag@Co by high temperature reduction2O3Composite material, i.e. Ag dopen Nano metal oxygen
Compound composite material.
A kind of preparation method of Ag@ZnO (90) composite material, comprising the following steps:
(1) by Zn(NO3)2·6H2O is mixed with the DMF solution of imidazoles -2- formaldehyde, and reaction obtains Z9 carrier material；
(2) Z9 carrier material being dispersed in silver nitrate solution, then stir process filters, and it is dry, obtain Ag@Z9 intermediate；
(3) obtained Ag@Z9 intermediate is obtained into Ag@ZnO (90) composite material, i.e. Ag dopen Nano gold by high temperature reduction
Belong to oxide composite.
Preferably, in step (1), Zn(NO3)2·6H2O, 2-methylimidazole, methanol mass ratio be (1~2): (3~4)
: (100~120), preferably 1.5: 3.3: 110；Co(NO3)2·6H2O, 2-methylimidazole, methanol mass ratio be (1~2): (9
~10): (140~150), preferably 1.9: 9.8: 143；Zn(NO3)2·6H2O, imidazoles -2- formaldehyde, DMF mass ratio be (6~
7): (2~3): (10 ~ 20), preferably 6.7: 2.9: 14.
The present invention is first using simple mild method preparation zeolite imidazole ester frame structure material as carrier material, tool
There are biggish specific surface area, uniform pore size, stably and controllable structure, and reproducible, can be used as one well
Container adulterates Nano silver grain, is a kind of good carrier material.
In above-mentioned technical proposal, in step (2), carrier material, silver nitrate mass ratio be 1: (0.5~1), preferably 1:
0.64；Stir process is to stir 12 hours at room temperature.
Ag nanoparticle precursor is attached to the table of zeolite imidazole ester frame structure material using simple method by the present invention
Face realizes the homogeneous distribution in surface-active site, helps to improve photocatalytic activity.
In above-mentioned technical proposal, in step (3), the atmosphere of high temperature reduction is hydrogen/argon gas mixed atmosphere, temperature 400
DEG C, time 5h；It is preferred that heating rate when high temperature reduction is 5 DEG C/min；In hydrogen/argon gas mixed atmosphere, the volume of hydrogen
Percentage is 3%.
The invention discloses the Ag doped with nano metal oxide composites prepared according to above-mentioned preparation method；The present invention
Ag nanoparticle is directly equably loaded to by nano-metal-oxide surface, the Ag of formation using simple in-situ reducing method
Nanoparticle is minimum, is conducive to constantly catalytic degradation tetracycline.
The present invention further discloses above-mentioned Ag doped with nano metal oxide composite or silver-colored carrier composite materials
Application in degradation tetracycline；Either above-mentioned Ag dopen Nano metal oxide composite or silver-colored carrier composite material exist
Application in the material of preparation degradation tetracycline.
The invention also discloses a kind of methods of tetracycline of degrading, comprising the following steps:
(1) salt is mixed with imidazolium compounds solution, reaction obtains carrier material；Salt is Zn(NO3)2·6H2O or Co
(NO3)2·6H2O；The imidazolium compounds is 2-methylimidazole or imidazoles -2- formaldehyde；
(2) carrier material is dispersed in silver nitrate solution, stir process, then filters, is dry, obtains silver-colored carrier composite wood
Material；
(3) obtained silver-colored carrier composite material is obtained into Ag dopen Nano metal oxide composite by high temperature reduction；
(4) Ag dopen Nano metal oxide composite is placed in the solution containing tetracycline, completes tetracycline under illumination
Degradation.
Ag doped with nano metal oxide composite is directly put into the tetracycline aqueous solution of 10mg/L by the present invention, is led to
Tetracycline is catalytically decomposed as CO the method for crossing illumination2、H2O etc., to achieve the effect that efficient degradation tetracycline；Illumination is too
Sunlight shines or simulated solar illumination.
Advantages of the present invention:
1, Nano silver grain is equably born in the nano metal oxide composite material of doping Nano silver grain disclosed by the invention
It is loaded in metal oxide surface, the size of 5-20nm may advantageously facilitate catalytic performance, be a kind of good loaded catalyst material
Material.
2, the preparation method of the nano metal oxide composite material of doping Nano silver grain disclosed by the invention is simple, bears
Carrying capacity is controllable, and reproducible；The Ag nanoparticle of formation is minimum, equably loads to metal oxide surface；In photocatalysis
There is preferable degradation rate during degradation tetracycline.
3, the preparation method of the nano metal oxide composite material of doping Nano silver grain disclosed by the invention operates letter
It is single, overcome the defect for the supported catalyst that the prior art needs complicated preparation method that can just prepare homogeneous distribution；Especially
It is that the product of so simple preparation method preparation has the performance of excellent degradation tetracycline, is especially advantageous for industrial applications.
Detailed description of the invention
Fig. 1 is the X ray diffracting spectrum of Z8, Z6, Z9, Ag@Z8, Ag@Z6, Ag@Z9；
Fig. 2 is transmission electron microscope picture (TEM) (a) Z8 of carrier material and silver-colored carrier composite material；(b) Z6；(c) Z9；(d)
Ag@Z8；(e) Ag@Z6；(f) Ag@Z9；
Fig. 3 is Ag@ZnO (8), Ag@Co2O3With the X ray diffracting spectrum (a) and transmission electron microscope picture (TEM) (b) of Ag@ZnO (90)
Ag@ZnO(8)；(c)Ag@Co2O3；(d) Ag@ZnO (90)；
Fig. 4 is Ag@Z8, Ag@Z6, the effect picture (a) of Ag@Z9 catalytic degradation tetracycline (0.010 mg/mL) and dynamics are quasi-
It closes curve (b)；
Fig. 5 is Ag@MO(metal oxide) to ultraviolet-visible absorption spectra figure, degradation effect and the dynamic behavior of tetracycline degradation
(a) Ag@ZnO (8)；(b) Ag@Co2O3；(c) Ag@ZnO(90)；(d)Ag@ZnO(8),Ag@Co2O3, Ag@ZnO catalysis drop
The effect picture of solution；(e) dynamic fitting curve；
Fig. 6 is tetracycline in silver-colored carrier composite material, Ag dopen Nano metal oxide composite photocatalytic degradation
Reperformance test (a) Ag@Z8；(b)Ag@Z6；(c)Ag@Z9；(d)Ag@ZnO(8)；(e)Ag@Co2O3；(f)Ag@ZnO(90).
Specific embodiment
The invention discloses the preparation methods of Ag dopen Nano metal oxide composite, comprising the following steps:
(1) salt is mixed with imidazolium compounds solution, reaction obtains carrier material；Salt is Zn(NO3)2·6H2O or Co
(NO3)2·6H2O；The imidazolium compounds is 2-methylimidazole or imidazoles -2- formaldehyde；
(2) carrier material is dispersed in silver nitrate solution, stir process, then filters, is dry, obtains silver-colored carrier composite wood
Material；
(3) obtained silver-colored carrier composite material is obtained into Ag dopen Nano metal oxide composite by high temperature reduction.
The preparation of one carrier material of embodiment, the specific steps are as follows:
3.30g 2-methylimidazole (Hmin) is dissolved in 70ml methanol, 1.50gZn(NO is added to3)2·6H2The 70ml methanol of O
It in solution, is sufficiently mixed, stirs 12h at room temperature；Reaction solution is put into vacuum oven after filtering, and vacuumizes, 95 DEG C of baking 12h, i.e.,
Obtain Z8.
9.80g 2-methylimidazole (Hmin) is dissolved in 100ml methanol, 1.91gCo(NO is added to3)2·6H2O's
It in 100ml methanol solution, is sufficiently mixed, stirs at room temperature for 24 hours；Reaction solution is by being centrifuged at a high speed, and methanol is washed, and ethyl alcohol is washed
Afterwards, it is put into vacuum oven, is vacuumized, 80 DEG C are dried for 24 hours to get Z6.
0.29g imidazoles -2- formaldehyde is dissolved in 15ml DMF, 0.67g Zn(NO is added to3)2·6H2The 15mlDMF of O is molten
It in liquid, is sufficiently mixed, stirs 12h at room temperature；Reaction solution after methanol is washed, is put into vacuum oven, takes out by being centrifuged at a high speed
Vacuum, 90 DEG C of baking 10h are to get Z9.
The TEM that attached drawing 2a is Z8 schemes, and the TEM that attached drawing 2b is Z6 schemes, and the TEM that attached drawing 2c is Z9 schemes, as can be seen from the figure
Carrier material has good crystal structure, shows regular hexagon shape crystal grain, and size is about 200 nm.
The preparation of two silver medal carrier composite material of embodiment, the specific steps are as follows:
The carrier material powder of the above-mentioned preparation of 0.1g is dispersed in 7mL 53.7mmol/L silver nitrate (~ 63.9mg) solution respectively
In (volume ratio: water: methanol=1:6), 12h is stirred at room temperature, then filters, it is dry, silver-colored carrier composite material is obtained, respectively
For Ag@Z8, Ag@Z6 and Ag@Z9.
The TEM that attached drawing 2d is Ag Z8 schemes, and the TEM that attached drawing 2e is Ag Z6 schemes, and the TEM that attached drawing 2f is Ag Z9 schemes, Cong Tuzhong
It can be seen that the surface of silver-colored carrier composite material relatively evenly distributed Ag nanoparticle, and Ag particle is relatively small.Due to
Carrier material substrate is different, the silver-colored carrier composite material structure of formation also difference.As the Ag nanoparticle in Ag@Z8 is opposite
It is more evenly tiny, about 5nm or so, and since organic ligand is different, the Ag nano-particles size in Ag@Z9 is relatively larger,
About 20nm.
Three Ag@MO(Ag dopen Nano metal oxide composite of embodiment) preparation, the specific steps are as follows:
Silver-colored carrier composite material obtained above is dispersed in porcelain boat, is put into tube furnace, is containing 3vol%H2Ar atmosphere
Under calcined, obtain Ag@MO(Ag dopen Nano metal oxide composite), respectively Ag@ZnO (8), Ag@Co2O3With
Ag@ZnO(90)；5 DEG C/min of heating rate, calcination time 5h, 400 DEG C of calcination temperature.
The TEM that attached drawing 3b is Ag@ZnO (8) schemes, and attached drawing 3c is Ag@Co2O3TEM figure, attached drawing 3d is Ag@ZnO (90)
, as can be seen from the figure there is uniformly tiny Ag nanoparticle on (8) surface Ag@ZnO in TEM figure, and in Ag@Co2O3With Ag@
ZnO (90) surface is also dispersed with Ag particle.
The present invention constructs a series of carrier materials, and the method by introducing silver and high-temperature calcination has synthesized six kinds of differences
Composite A g@Z8, Ag@Z6, Ag@Z9, Ag@ZnO (8), Ag@Co2O3With Ag@ZnO (90), X ray diffracting spectrum is shown in figure
1.These materials are used equally for the catalytic degradation of tetracycline aqueous solution under visible light.
Example IV is by Ag@MO(Ag dopen Nano metal oxide composite) it is used for photocatalytic degradation tetracycline
By the photochemical catalyst (Ag dopen Nano metal oxide composite, silver-colored carrier composite material) point for the 50mg being ready for
It is not distributed in the tetracycline of 100ml 10mg/L, stirs, adsorbed under the conditions of dark reaction, reach after about 30 minutes
Adsorption equilibrium；Then solution is irradiated with simulated solar radiant xenon lamp, solution (3mL) is sampled every 15 minutes, directly
Terminate to degradation.
The tetracycline taken centrifuge is separated into (7000 rpm 8 minutes), and passes through Millipore filter (hole
Diameter: 0.22 μm, water-soluble) filtering, remove remaining catalyst.Supernatant liquor is taken, ultraviolet test is carried out.After reaction, it urges
Agent is recycled.
Attached drawing 4 is to carry out photocatalysis using different silver-colored carrier composite materials under conditions of tetracycline solubility is certain
The variation schematic diagram and dynamic fitting curve of degradation.Carry out dynamic analysis by degradation behavior to catalyst it is found that
Under the same terms, Ag@Z8, Ag@Z6, Ag@Z9 degrade 68.2%, 63.6% respectively, 65.2% TC；The TC concentration decline of catalysis
Kinetics Rate Constants By Using k be respectively 0.34839,0.31587,0.33955；Z8, Z6, Z9 degrade less than 10% to tetracycline；It presses
41.3% is degraded to tetracycline according to the TiO 2 carrying Argent grain of 2 method of CN104304319A embodiment preparation.
Attached drawing 5 be Ag@MO(Ag dopen Nano metal oxide composite) degradation tetracycline ultraviolet test knot
Fruit, degradation effect and dynamic behavior.As can be seen from the figure the tetracycline removal rate of Ag@ZnO (8) and Ag@ZnO (90) is basic
It is close, it can achieve 83.6% and 83.7% or so.And its dynamic behavior is analyzed it is found that using Ag@MO degradation TC's
Concentration decline process meets dynamic analysis, and degradation is controlled by diffusion substantially.
Embodiment five
It is degraded in triplicate tetracycline with Ag@Z8, Ag@Z6, Ag@Z9, and with Ag@ZnO (8), Ag@Co2O3、Ag@ZnO
(90) degradation tetracycline is repeated five times, effect shows such as Fig. 6.It can be seen from the figure that compared with first time runs,
The degradation efficiency of Ag@MO still can keep 97.4% after five circulations, show that there is the Ag@MO catalyst good repeat to make
The property used.
By analyzing above, Ag@ZnO has best visible absorption effect, doping disclosed by the invention after high-temperature calcination
The preparation method of the nano metal oxide composite material of Nano silver grain is easy to operate, overcomes the prior art and needs complexity
Preparation method can just prepare the defect of the supported catalyst of homogeneous distribution；The production of especially so simple preparation method preparation
Product have the performance of excellent degradation tetracycline, are especially advantageous for industrial applications.
Claims (10)
1. a kind of Ag dopen Nano metal oxide composite, which is characterized in that the Ag dopen Nano metal oxide is multiple
The preparation method of condensation material the following steps are included:
(1) salt is mixed with imidazolium compounds solution, reaction obtains carrier material；Salt is Zn(NO3)2•6H2O or Co(NO3)2•
6H2O；The imidazolium compounds is 2-methylimidazole or imidazoles -2- formaldehyde；
(2) carrier material is dispersed in silver nitrate solution, stir process, then filters, is dry, obtains silver-colored carrier composite wood
Material；
(3) obtained silver-colored carrier composite material is obtained into Ag dopen Nano metal oxide composite by high temperature reduction.
2. Ag dopen Nano metal oxide composite according to claim 1, which is characterized in that in step (1), work as salt
For Zn(NO3)2•6H2O, when imidazolium compounds is 2-methylimidazole, Zn(NO3)2•6H2O, the mass ratio of 2-methylimidazole be (1~
2): (3~4), the temperature of reaction are room temperatures, and the time is 12 hours；When salt is Zn(NO3)2•6H2O, imidazolium compounds is imidazoles-
When 2- formaldehyde, Zn(NO3)2•6H2O, the mass ratio of imidazoles -2- formaldehyde is (6~7): (2~3), the temperature of reaction are room temperatures, when
Between be 10 hours；When salt is Co(NO3)2•6H2O, when imidazolium compounds is 2-methylimidazole, Co(NO3)2•6H2O, 2- methyl miaow
The mass ratio of azoles is (1~2): (9~10), and the temperature of reaction is room temperature, and the time is 24 hours.
3. Ag dopen Nano metal oxide composite according to claim 1, which is characterized in that in step (2), carrier
Material, silver nitrate mass ratio be 1: (0.5~1)；Stir process is to stir 12 hours at room temperature.
4. Ag dopen Nano metal oxide composite according to claim 1, which is characterized in that in step (3), high temperature
The atmosphere of reduction is hydrogen/argon gas mixed atmosphere, and temperature is 400 DEG C, time 5h；Heating rate when high temperature reduction is 5 DEG C/
Minute；In hydrogen/argon gas mixed atmosphere, the percentage by volume of hydrogen is 3%.
5. it is a kind of silver carrier composite material, which is characterized in that it is described silver carrier composite material preparation method the following steps are included:
(1) salt is mixed with imidazolium compounds solution, reaction obtains carrier material；Salt is Zn(NO3)2•6H2O or Co(NO3)2•
6H2O；The imidazolium compounds is 2-methylimidazole or imidazoles -2- formaldehyde；
(2) carrier material is dispersed in silver nitrate solution, stir process, then filters, is dry, obtains silver-colored carrier composite wood
Material.
6. silver-colored carrier composite material according to claim 5, which is characterized in that in step (1), when salt is Zn(NO3)2•
6H2O, when imidazolium compounds is 2-methylimidazole, Zn(NO3)2•6H2O, the mass ratio of 2-methylimidazole is (1~2): (3~4),
The temperature of reaction is room temperature, and the time is 12 hours；When salt is Zn(NO3)2•6H2O, when imidazolium compounds is imidazoles -2- formaldehyde, Zn
(NO3)2•6H2O, the mass ratio of imidazoles -2- formaldehyde is (6~7): (2~3), and the temperature of reaction is room temperature, and the time is 10 hours；
When salt is Co(NO3)2•6H2O, when imidazolium compounds is 2-methylimidazole, Co(NO3)2•6H2O, the mass ratio of 2-methylimidazole is
(1~2): (9~10), the temperature of reaction are room temperatures, and the time is 24 hours.
7. silver-colored carrier composite material according to claim 5, which is characterized in that in step (2), carrier material, silver nitrate
Mass ratio is 1: (0.5~1)；Stir process is to stir 12 hours at room temperature.
8. the Ag dopen Nano metal oxide described in preparation claim 1 of silver carrier composite material described in claim 5 is compound
Application in material.
9. silver carrier composite wood described in Ag dopen Nano metal oxide composite or claim 5 described in claim 1
Expect the application in degradation tetracycline；Either Ag dopen Nano metal oxide composite or right described in claim 1
It is required that application of the 5 silver-colored carrier composite materials in the material of preparation degradation tetracycline.
10. application as claimed in claim 9, which is characterized in that degradation tetracycline carries out under light illumination.
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