CN109589984A - A kind of preparation method and applications of double reaction channel photochemical catalysts - Google Patents
A kind of preparation method and applications of double reaction channel photochemical catalysts Download PDFInfo
- Publication number
- CN109589984A CN109589984A CN201811515378.XA CN201811515378A CN109589984A CN 109589984 A CN109589984 A CN 109589984A CN 201811515378 A CN201811515378 A CN 201811515378A CN 109589984 A CN109589984 A CN 109589984A
- Authority
- CN
- China
- Prior art keywords
- solution
- reaction channel
- photochemical catalysts
- preparation
- double reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 75
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 61
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000004098 Tetracycline Substances 0.000 claims abstract description 24
- 229960002180 tetracycline Drugs 0.000 claims abstract description 22
- 229930101283 tetracycline Natural products 0.000 claims abstract description 22
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 22
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 22
- 235000019441 ethanol Nutrition 0.000 claims abstract description 21
- 238000006473 carboxylation reaction Methods 0.000 claims abstract description 15
- 239000011651 chromium Substances 0.000 claims abstract description 14
- 238000001291 vacuum drying Methods 0.000 claims abstract description 10
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 7
- 239000012265 solid product Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 6
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims abstract description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 6
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002604 ultrasonography Methods 0.000 claims abstract description 4
- 229910001308 Zinc ferrite Inorganic materials 0.000 claims description 29
- 229960004756 ethanol Drugs 0.000 claims description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 230000021523 carboxylation Effects 0.000 claims description 8
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 238000010828 elution Methods 0.000 claims description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 230000001360 synchronised effect Effects 0.000 claims description 4
- -1 4-vinylpridine Chemical compound 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 239000012456 homogeneous solution Substances 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 30
- 230000009467 reduction Effects 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 12
- 229910001430 chromium ion Inorganic materials 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 239000011259 mixed solution Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000000593 degrading effect Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 description 31
- 238000006722 reduction reaction Methods 0.000 description 23
- 238000000034 method Methods 0.000 description 19
- 238000006731 degradation reaction Methods 0.000 description 16
- 230000015556 catabolic process Effects 0.000 description 14
- 239000010410 layer Substances 0.000 description 14
- 238000001179 sorption measurement Methods 0.000 description 14
- 230000001699 photocatalysis Effects 0.000 description 12
- 238000007146 photocatalysis Methods 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000013019 agitation Methods 0.000 description 7
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000005273 aeration Methods 0.000 description 5
- 238000007664 blowing Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000003115 biocidal effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 3
- KSPIHGBHKVISFI-UHFFFAOYSA-N Diphenylcarbazide Chemical compound C=1C=CC=CC=1NNC(=O)NNC1=CC=CC=C1 KSPIHGBHKVISFI-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 235000011056 potassium acetate Nutrition 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 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
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J35/33—Electric or magnetic 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
- B01J35/30—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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (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 environmentally conscious materials synthesis technical fields, and in particular to a kind of preparation method and application of double reaction channel photochemical catalysts.Specific steps: by the ZnFe of carboxylation2O4It is added in the mixed solution of water and ethyl alcohol, mechanical stirring, K is added2Cr2O7, 4-vinylpridine, EGDMA and AIBN is added in ultrasound, and it is ultrasonic, it transfers the solution into quartz glass flask, P123 is added, is placed in microwave reaction instrument, stir, washing, vacuum drying obtains solid product；Then, P123 is removed, elutes hexavalent chromium with EDTA, magnet separation rinses, is dried to obtain product；The material property of can choose of the invention ground reduction of hexavalent chromium ion while tetracycline of degrading.
Description
Technical field
The invention belongs to environmentally conscious materials synthesis technical fields, and in particular to a kind of preparation side of double reaction channel photochemical catalysts
Method and its selective reduction Cr6+And the application of synchronous photocatalytic degradation tetracycline.
Background technique
Nowadays, environmental pollution is the topic that people discuss warmly, even more all circles' social people problem urgently to be resolved, and is successfully ground
It sends out and environmental protection and economy is widely used efficient method solves the common objective that problem of environmental pollution is for everybody again.It is well known that
Pollutant kind present in water environment is various and complicated, in recent years, because the antibiotic and heavy metal ion of residue in water are exceeded
And the human health problems and environmental problem caused are continually reported.Tetracycline is a kind of common antibiotic, people's
It is widely used in daily life, however, abuse tetracycline not only results in a large amount of residual contaminants and is discharged into water body, causes
Negative effect to water environment can also inhibit the progress of many water process.Moreover, hexavalent chromium is considered most malicious
One of harmful heavy metal ion, it has the characteristics that biological non-degradable, this makes common sewage treatment process efficient
Ground removes hexavalent chromium, thus it easily enters human body, causes extremely serious harm.And the chromium ion toxicity of reduction-state is wanted
Much smaller than the chromium ion of sexavalence, therefore in view of tetracycline and Cr VI are to the pollution of environment and the harm of human body, selectively
Reduction of hexavalent chromium ion is simultaneously while tetracycline of degrading is provided with highly important research significance.So design being capable of simultaneous selection
Property in reduction of hexavalent chromium ion and water of degrading tetracycline material it is challenging and innovative.
Photocatalysis technology is considered as a kind of effective environmental protection solution due to the advantages that its energy-saving and environmental protection and low cost
Scheme.Antibiotic is oxidized to that bio-toxicity is smaller and the substance of easily biological-degradable by photocatalytic degradation method, or even they are turned
Harmless compounds are turned to, its degradation range and effect are superior to common sewage treatment process to a certain extent.Photocatalysis is also
The highly toxic metal ion of high-valence state can be reduced to the ion of lower valency hypotoxicity by original method, can make it in terms of toxicity
It is effectively controlled.The photochemical catalyst of photocatalysis field design at present is many kinds of, but is all difficult to avoid that photocatalysis effect is poor, light
The defects of stability is poor, photoresponse section is short, photo-generate electron-hole is easily compound.
On the other hand, for selective reduction hexavalent chromium, it is necessary first to which realization is selected in the ion of numerous high concentrations
It is adsorbed to selecting property, to introduce ionic imprinting technique.Ionic imprinting technique is the extension of molecular imprinting technology, it is one
It is largely template in ion imprinted polymer that kind generates the technology of recognition site using template ion in macromolecular matrices
The imprinted cavity of ion design is uniformly distributed, these holes are consistent with the shape of template ion, size and functional group.Therefore, from
Sub- imprinted polymer has specific ion identification ability and higher binding affinity to template ion.
In the past few years, for photochemical catalyst as processing organic pollutants and heavy metal ion, ion blotting is poly-
It closes object to have received widespread attention as the research of the selective absorbent of template ion, utilizes the realization pair simultaneously of light-catalysed mechanism
The degradation of organic matter and the great meaning of the reduction of heavy metal ion, however, photocatalysis and the effective of ionic imprinting technique combine in fact
The research of processing multiple pollutant and reducing heavy metal is also rarely reported in complicated water environment now.In addition, as far as we know,
Double reaction channels, which are based on, in conjunction with photocatalysis technology and ionic imprinting technique realizes that selective reduction heavy metal ion is simultaneously degraded simultaneously
Antibiotic residue is unprecedented.
Summary of the invention
In order to solve the easily compound defect of photo-generate electron-hole of photochemical catalyst generation, present invention introduces conductive
Imprinted layer enables light induced electron to shift easily, while electrons and holes can carry out respectively in different reaction channels
Light degradation and reduction reaction, greatly improve photocatalysis efficiency.
Present invention firstly provides a kind of double reaction channel photochemical catalysts, with ZnFe2O4For matrix photochemical catalyst, ion is utilized
Engram technology coats ion blotting layer on its surface；There are a large amount of mesopore orbit and hexavalent chromium print on the ion blotting layer
Mark hole；By 0.05g, double reaction channel photochemical catalysts are used for the photocatalytic degradation of the tetracycline of 100mL 20mg/L,
The simulated solar irradiation of 1h irradiates lower palliating degradation degree C/C0It is 0.416；In addition, double reaction channel photochemical catalysts are used for by 0.05g
The Cr of 100mL10mg/L6+And Ag+In mixed solution, 150.43mg/g is up to the adsorption capacity of hexavalent chromium in material 1h,
To the reduction rate of hexavalent chromium up to 92.67% in 2h.
The present invention also provides a kind of preparation methods of double reaction channel photochemical catalysts, carry out as steps described below:
Step 1:ZnFe2O4Synthesis:
Firstly, by FeCl3·6H2O and ZnCl2It is dissolved in ethylene glycol, using magnetic stirrer to clear solution, adds
Enter potassium acetate, continues mechanical stirring to uniform, then transfer the solution into autoclave and react, later, collect black with magnet
Product and with distilled water and ethanol washing for several times, finally, vacuum drying obtains final sample at room temperature.
Step 2:ZnFe2O4It is carboxy-modified:
Firstly, by ZnFe2O4Powder is dispersed in ultrasound a period of time in distilled water, after forming homogeneous solution, by citric acid
It is added in above-mentioned solution, under the atmosphere of nitrogen for a period of time in preference temperature mechanical stirring, the sediment magnetic that will be obtained
Iron separates and uses distilled water and ethanol washing for several times, is then dried in vacuo up to carboxylation ZnFe2O4。
Step 3: the synthesis of double reaction channel photochemical catalysts:
Firstly, by the ZnFe of carboxylation2O4It is added in ethanol solution, at room temperature mechanical stirring, is denoted as solution A；Meanwhile
By K2Cr2O7Ethanol solution is dissolved in be ultrasonically treated, solution uniformly after sequentially add 4-vinylpridine, EGDMA and
AIBN continues ultrasonic disperse, until completing dissolution, is denoted as solution B；Solution A and solution B are finally transferred to quartz glass jointly
In flask and P123 is added, is placed in microwave reaction instrument and is reacted, after reaction after container is cooled to room temperature, passes through magnetic
Iron separates and collects final product, and is washed with dehydrated alcohol and deionized water and remove excessive solvent, and vacuum drying will be resulting
Solid product carries out the removal of P123 with acetone in cable type extractor according, then, elutes hexavalent chromium with EDTA, then use magnet
Separation is then rinsed with distilled water and ethyl alcohol to neutrality, vacuum drying, obtains double reaction channel photochemical catalysts.
In step 1, the FeCl3·6H2O、ZnCl2, ethylene glycol and potassium acetate amount ratio be 4mmol:2mmol:
15mL:40mmol, the mixing time 30min of magnetic agitation, reaction temperature of the autoclave in vacuum oven are 180 DEG C, instead
For for 24 hours, churned mechanically revolving speed is 600rpm/min between seasonable.
In step 2, the ZnFe2O4The amount ratio of powder, citric acid and distilled water is 2g:1g:50mL, ultrasonic time
For 30min；The churned mechanically time is 1h, and reaction condition is 60 DEG C, is carried out in oil bath pan, churned mechanically revolving speed is
600rpm/min。
In step 1~2, the vacuum drying temperature is 30 DEG C, and drying time is 12h.
In step 3, in solution A, the ZnFe of the carboxylation2O4Amount ratio with ethanol solution is 0.3g:40mL, wherein
The volume ratio of water and ethyl alcohol is 5:3 in ethanol solution.
In step 3, in solution B, the K2Cr2O7, ethyl alcohol, 4-vinylpridine, EGDMA and AIBN amount ratio be
1mmol:10mL:5mmol:5mmol:0.04g.K2Cr2O7Amount ratio with P123 is 1mmol:1.5g.
When solution A and solution B mix, the ZnFe of carboxylation2O4、K2Cr2O7Amount ratio be 0.3g:1mmol.
In step 3, the ultrasonic time is 30min.
In step 3, the reaction power in the microwave reaction instrument is 600W, and operating temperature is 70 DEG C, the working time 90
Minute, mixing speed is 2000 revs/min.
In step 3, the amount ratio of the solid product and acetone is 0.5g:100mL；The temperature of elution is 60 DEG C, elution
Time be for 24 hours.
In step 3, the concentration of the EDTA is 0.5g/L.
In step 3, the vacuum drying temperature is 30 DEG C, and drying time is 12h.
Binary channels photochemical catalyst of the invention is with ZnFe2O4For matrix, one layer of selective ion is coated on its surface
Imprinted layer has a large amount of mesopore orbits and object ion Cr on the ion blotting layer6+Trace hole to constituting binary channels, together
When function monomer electric conductivity, electrons and holes can be efficiently separated, keep degradation reaction and reduction reaction logical in different reactions
It is carried out in road.
Double reaction channel photochemical catalysts prepared by the present invention are used to restore Cr based on differential responses channel selectivity6+And it is same
Walk the purposes of photocatalytic degradation tetracycline.
Beneficial effects of the present invention:
(1) double reaction channel photochemical catalysts prepared by the present invention are since there are a large amount of hexavalent chromium traces in imprinted layer
Hole, so that prepared double reaction channel photochemical catalysts have the ability of selective absorption hexavalent chromium, for Cr VI
The adsorption capacity of ion can achieve 150.43mg/g, much higher than the adsorption capacity of silver ion, also be much higher than other materials pair
The adsorption capacity of hexavalent chromium shows superior selectivity.
(2) double reaction channel photochemical catalysts prepared by the present invention are due to mesoporous and conductive traces layer presence, so that made
Standby double reaction channel photochemical catalysts can generate different reaction channel and realize simultaneously to the degradation of tetracycline and copper ion
Reduction.
(3) double reaction channel photochemical catalysts prepared by the present invention use 4- ethylene during the introducing of ion blotting layer
Yl pyridines enable light induced electron freely to shift on ion blotting layer as function monomer since its is conductive, suppression
It is compound again with hole to make it, hexavalent chromium is reduced on trace hole, in addition to this, ZnFe2O4It generates
The tetracycline that hole can degrade through mesoporous entrance, so that degradation reaction and reduction reaction are in two different reaction channels
It carries out, improves photocatalysis efficiency.
(4) the double reaction channel photochemical catalyst property of can choose reduction of hexavalent chromium ions prepared by the present invention and synchronous degradation four
Ring is plain, not yet has been reported that currently with the photocatalysis material for light degradation and selective reduction synchronous with ionic imprinting technique,
So material prepared by the present invention is unique and innovative, and there is low cost, high usage, with strong points, effect
Good advantage.
Detailed description of the invention
Fig. 1 is the XRD spectra of different samples, a ZnFe2O4, b be carboxylation ZnFe2O4, c be double reaction channel photocatalysis
Agent.
Fig. 2 is the FT-IR spectrogram of different samples, a ZnFe2O4, b be carboxylation ZnFe2O4, c be double reaction channel photocatalysis
Agent.
Fig. 3 is the SEM spectrogram (a) of double reaction channel photochemical catalysts, and TEM spectrogram (b), HR-TEM spectrogram (c) and SAED are composed
Scheme (d).
Fig. 4 is nitrogen adsorption-desorption isotherm of different samples, a ZnFe2O4Nitrogen adsorption-desorption isotherm, b be
Nitrogen adsorption-desorption isotherm of double reaction channel photochemical catalysts, nitrogen adsorption-desorption that c is non-mesoporous non-imprinted polymer
Thermoisopleth, d ZnFe2O4Average pore size distribution curve, average pore size distribution curve, the f that e is double reaction channel photochemical catalysts
For the average pore size distribution curve of non-mesoporous non-imprinted polymer.
Fig. 5 is the magnetization curve of different samples, a ZnFe2O4, b be double reaction channel photochemical catalysts.
Fig. 6 is photochemical catalyst dispersity a of the present invention and magnet adsorbed state b.
Fig. 7 is that different samples investigate figure, a ZnFe to the light degradation of tetracycline2O4, b be double reaction channel photochemical catalysts, c
For non-mesoporous non-imprinted polymer.
Fig. 8 is that different samples investigate figure, a ZnFe to hexavalent chromium selective reduction2O4, b be that double reaction channel light are urged
Agent, c are non-mesoporous non-trace photopolymer.
Fig. 9 is double reaction channel photochemical catalyst study on the stability figures.
Specific embodiment
Below with reference to specific implementation example, the present invention will be further described.
The evaluation of tetracycline adsorption activity: it is carried out in DW-01 type photochemical reactor, by the tetracycline of 100mL 20mg/L
Solution is added in reactor and measures its initial value, and the sample of 0.05g, source of not opening the light then is added, and set temperature is 30 DEG C, no
It opens the light irradiation, blowing air (aeration quantity 2mL/min) is opened magnetic agitation (revolving speed 600rpm/min), interval 10min sampling
Analysis, measures its concentration by ultraviolet-visible spectrophotometer, and pass through formula: Q=(C0- C) V/m calculates its adsorption capacity
Q, wherein C0For the initial concentration of tetracycline, C is the concentration of tetracycline when reaching adsorption equilibrium, and V is the volume of solution,
M is the quality for the sample being added.
The evaluation of hexavalent chromium adsorption activity: it is carried out in DW-01 type photochemical reactor, by the six of 100mL 10mg/L
Valence chromium ion solution is added in reactor and measures each initial value, and the sample of 0.05g, source of not opening the light, set temperature is then added
It is 30 DEG C, irradiation of not opening the light, blowing air (aeration quantity 2mL/min) is opened magnetic agitation (revolving speed 600rpm/min), interval
10min sampling analysis measures its concentration by diphenylcarbazide method, and passes through formula: Q=(C0- C) V/m calculate its absorption hold
Q is measured, wherein C0For the initial concentration of hexavalent chromium, C is the concentration of hexavalent chromium when reaching adsorption equilibrium, and V is solution
Volume, m be added sample quality.
Photocatalytic activity evaluation: carrying out in DW-01 type photochemical reactor, and 100mL 20mg/L tetracycline is molten
Liquid is added in reactor and measures its initial value, and the sample of 0.05g, source of not opening the light then is added, and set temperature is 30 DEG C, does not open
Light irradiation, blowing air (aeration quantity 2mL/min) are opened magnetic agitation (revolving speed 600rpm/min), after reaching adsorption equilibrium,
It is irradiated again with simulated solar irradiation, open magnetic agitation (revolving speed 600rpm/min) and opens aerator and be passed through air (flow
For 2mL/min), set temperature is 30 DEG C, and 10min sampling analysis is spaced in During Illumination, passes through ultraviolet-visible spectrophotometer
Its concentration is measured, and passes through formula: C/C0Its light degradation degree is calculated, wherein C0To reach tetracycline when adsorption equilibrium
Concentration, C be t moment measurement tetracycline concentration, t is the reaction time.
Selective absorption evaluation: carrying out in DW-01 type photochemical reactor, by 100mL 10mg/L hexavalent chromium and
Silver ion mixed solution is added in reactor and measures its initial value, and the sample of 0.05g, source of not opening the light, setting temperature is then added
Degree is 30 DEG C, irradiation of not opening the light, and blowing air (aeration quantity 2mL/min) is opened magnetic agitation (revolving speed 600rpm/min),
It is spaced 10min sampling analysis in the process, by the concentration of diphenylcarbazide method determination of hexavalent chromium ion, it is dense that ICP measures silver ion
Degree, and pass through formula: Q=(C0- C) V/m calculates the adsorption capacity of each ion, wherein C0For the initial concentration of specific ion, C is
The concentration of specific ion when reaching adsorption equilibrium, V are the volume of solution, and m is the quality for the sample being added.
Selective reduction evaluation: carrying out in DW-01 type photochemical reactor, by 100mL 10mg/L hexavalent chromium and
Silver ion mixed solution is added in reactor and measures its initial value, and the sample of 0.05g, source of not opening the light, setting temperature is then added
Degree is 30 DEG C, irradiation of not opening the light, and blowing air (aeration quantity 2mL/min) is opened magnetic agitation (revolving speed 600rpm/min), reached
It to after adsorption equilibrium, turns on light and irradiates 2h, sampling analysis after irradiation passes through the dense of diphenylcarbazide method determination of hexavalent chromium ion
Degree, ICP measures concentration of silver ions, and passes through formula: R=(C0-C)/C0The reduction rate of each ion is calculated, wherein C0For it is specific from
The initial concentration of son, C is the concentration of specific ion after reaching illumination 2h.
Embodiment 1:
(1)ZnFe2O4Synthesis: by 4.325g FeCl3·6H2O and 1.09g ZnCl2It is dissolved in 60mL ethylene glycol and mixing
Uniformly, then the potassium acetate of 2.453g is added in solution and is stirred 30 minutes, then transfer the solution into autoclave and
It is kept for 24 hours at 180 DEG C.Finally, for several times with magnet collection black product and with distilled water and ethanol washing, finally, sample is in room
Temperature is lower to be dried in vacuo 12h；
(2) carboxylation ZnFe2O4Synthesis: firstly, by 3g ZnFe2O4Powder is dispersed in 100mL deionized water, ultrasound point
It dissipates, after forming homogeneous solution, 1.5g citric acid is added in above-mentioned solution, under nitrogen protection in 60 DEG C of mechanical stirrings
Obtained sediment is separated with magnet and is used deionized water and ethanol washing for several times, is then dried in vacuo at 30 DEG C by 1h
12h；
(3) synthesis of double reaction channel photochemical catalysts: by the ZnFe of 0.6g carboxylation2O4Be added to 50mL deionized water and
In the mixed solution of the ethyl alcohol of 30mL, 30min is then continuously stirred at room temperature, is denoted as solution A.By 0.5884g K2Cr2O7It is molten
It in the ethanol solution of 20mL, is ultrasonically treated, 1.0514g 4-vinylpridine and 1.9893gEGDMA is added in the process, surpassed
Sound 30min is then added 0.08g AIBN into above-mentioned solution, and is stirred at room temperature.It is eventually adding 3g P123.It shifts
The mixture arrived is put into microwave reaction instrument to quartz container.Operating power is 600W, and operating temperature is 70 DEG C, work
Time is 90min, and mixing speed is 2000 revs/min, after reaction after container is cooled to room temperature, is separated and is received by magnet
Collect final product, and washed three times with dehydrated alcohol and deionized water and remove excessive solvent, then by solid product at 30 DEG C
Vacuum drying oven in dry 12h；
Dry solid product carries out P123 removal with acetone extract at 60 DEG C in cable type extractor according for 24 hours, after removal,
Sample is rinsed with 100mL 0.5g/L EDTA and is transferred in flask to elute hexavalent chromium, and then machinery stirs at 30 DEG C
12h is mixed, solid sample is separated with magnet, is then rinsed with distilled water and ethyl alcohol to neutral (pH=7), finally, by solid sample
The dry 12h in 30 DEG C of vacuum drying oven.
(4) synthesis of non-mesoporous non-trace photochemical catalyst: it is consistent with the method for (3), it saves and P123 and removal P123 is added
The step of and be added K2Cr2O7The step of with elution hexavalent chromium.
Fig. 1 is the XRD spectra of different samples, as can be seen from the figure: ZnFe2O46 diffraction maximums be located at
29.91 °, 35.23 °, 42.81 °, 53.10 °, 56.60 ° and 62.14 °, these values correspond respectively to ZnFe2O4(220),
(311), (400), (422), (511) and (440) crystal face.Further compare carboxylation ZnFe2O4With double reaction channel photochemical catalysts
XRD spectra illustrates that ion blotting layer is successfully coated on ZnFe it can be found that not extra peak increases or decreases2O4Surface,
And there is no the crystal forms for changing raw material.
Fig. 2 is the FT-IR spectrogram of different samples, as can be seen from the figure: carboxylation ZnFe2O4Compared to ZnFe2O4It has more
The peak of-COOH, illustrates that surface has successfully connected carboxyl.The double reaction channel photochemical catalysts of comparison can be seen that its peak and not only wrap
ZnFe is contained2O4Characteristic peak, further analysis can also find C-O, C=C and C-N, illustrate EGDMA and 4-vinylpridine
Presence, the presence of ion blotting layer is further proved, to show that double reaction channel photochemical catalysts successfully synthesize.
Fig. 3 is that SEM spectrogram (a), TEM spectrogram (b), HR-TEM spectrogram (c) and the SAED of double reaction channel photochemical catalysts are composed
Scheme (d), as can be seen from the figure: double reaction channel photochemical catalysts are prepared visibly homogeneous, and partial size is about 370nm, then passes through HR-
TEM figure is it can be seen that double reaction channel photocatalyst surfaces have organic layer cladding, while can carry out the ratio of crystal by SAED
It is right, it was demonstrated that ZnFe2O4Presence, this again shows that double reaction channel photochemical catalysts have been successfully synthesized.
Fig. 4 is the nitrogen adsorption desorption isotherm of different samples, it can be seen from the figure that double reaction channel photochemical catalysts have
There is maximum specific surface area, have benefited from a large amount of mesopore orbit in its surface and trace hole, in addition to this, its average pore size is also wanted
Less than ZnFe2O4With non-mesoporous non-trace photochemical catalyst, the presence of mesopore orbit and trace hole is demonstrated again that.
Fig. 5 be different samples magnetization curve, it can be seen that double reaction channel photochemical catalysts after coating imprinted layer still
With preferable magnetic saturation intensity, magnetic saturation intensity value is 49.27emu/g, and it is good to illustrate that double reaction channel photochemical catalysts have
Good Magneto separate characteristic.
A is the state that photochemical catalyst of the present invention disperses naturally in water in Fig. 6, and figure b is the state after magnet absorption.
Fig. 7 is that different samples investigate figure to the light degradation of tetracycline, as can be seen from the figure: ZnFe2O4To the drop of tetracycline
Solution degree highest, and double reaction channel photochemical catalysts are slightly less than ZnFe to the palliating degradation degree of tetracycline2O4, to illustrate imprinted layer
Cladding it is active without the light degradation for influencing photochemical catalyst.In addition to this, compare double reaction channel photochemical catalysts with it is non-mesoporous non-
The C/C of trace photochemical catalyst0It is found that having the material of the double reaction channels in mesoporous and trace hole to show more preferably Fourth Ring simultaneously
Plain degrading activity.
Fig. 8 is that different samples investigate figure to the selective reduction of hexavalent chromium, as can be seen from the figure: double reaction channels
Photochemical catalyst is up to 92.67% to the reduction rate of hexavalent chromium, is higher than reduction of the other materials to hexavalent chromium far away
Effect illustrates double reaction channel photocatalyst material surface a large amount of hexavalent chromium trace holes to the selectivity of hexavalent chromium
Absorption play the role of it is vital, and be conducive to its be further reduced.In addition to this, it can be seen that double reaction channel light are urged
Agent will be substantially better than silver ion for the reduction effect of hexavalent chromium.By comparing it is found that double reaction channel photochemical catalyst tables
The hexavalent chromium trace hole in face shows the specific recognition to hexavalent chromium, so can select in mixed solution
Property adsorbing hexavalent chromium ions are simultaneously reduced to trivalent chromic ion.And other materials can not show identical characteristic.
Fig. 9 is the study on the stability of double reaction channel photochemical catalysts, it can be seen from the figure that carrying out five light degradation respectively
The experiment of tetracycline and selective reduction hexavalent chromium, degradation rate and reduction rate illustrate double anti-without too big reduction
It answers channel photochemical catalyst that there is preferable stability, can be recycled for multiple times.
Claims (10)
1. a kind of preparation method of double reaction channel photochemical catalysts, which comprises the steps of:
By ZnFe2O4Powder is dispersed in ultrasound a period of time in distilled water, and after forming homogeneous solution, citric acid is added to
It states in solution, obtained sediment is separated with magnet and uses distilled water and ethanol washing by the mechanical stirring under the atmosphere of nitrogen
For several times, it is then dried in vacuo up to carboxylation ZnFe2O4；
By the ZnFe of carboxylation2O4It is added in ethanol solution, at room temperature mechanical stirring, is denoted as solution A；
Meanwhile by K2Cr2O7Ethanol solution is dissolved in be ultrasonically treated, solution uniformly after sequentially add 4-vinylpridine,
EGDMA and AIBN continues ultrasonic disperse, until completing dissolution, is denoted as solution B；
Solution A and solution B are finally transferred in quartz glass flask jointly and are added P123, is placed in microwave reaction instrument and carries out
Reaction separates and collects final product by magnet after reaction after container is cooled to room temperature, and with dehydrated alcohol and go from
Sub- water washing removes excessive solvent, and resulting solid product is carried out P123 with acetone by vacuum drying in cable type extractor according
Removal then elute hexavalent chromium with EDTA, then separated with magnet, then rinsed with distilled water and ethyl alcohol to neutrality, very
Sky is dry, obtains double reaction channel photochemical catalysts.
2. the preparation method of double reaction channel photochemical catalysts according to claim 1, which is characterized in that described in solution A
Carboxylation ZnFe2O4Amount ratio with ethanol solution is 0.3g:40mL, wherein the volume ratio of water and ethyl alcohol is in ethanol solution
5:3.
3. the preparation method of double reaction channel photochemical catalysts according to claim 1, which is characterized in that described in solution B
K2Cr2O7, ethyl alcohol, 4-vinylpridine, EGDMA and AIBN amount ratio be 1mmol:10mL:5mmol:5mmol:0.04g；
K2Cr2O7Amount ratio with P123 is 1mmol:1.5g.
4. the preparation method of double reaction channel photochemical catalysts according to claim 1, which is characterized in that solution A and solution B
When mixing, the ZnFe of carboxylation2O4、K2Cr2O7Amount ratio be 0.3g:1mmol.
5. the preparation method of double reaction channel photochemical catalysts according to claim 1, which is characterized in that the ultrasonic time
It is 30min.
6. the preparation method of double reaction channel photochemical catalysts according to claim 1, which is characterized in that the microwave reaction
Reaction power is 600W in instrument, and operating temperature is 70 DEG C, and the working time is 90 minutes, and mixing speed is 2000 revs/min.
7. the preparation method of double reaction channel photochemical catalysts according to claim 1, which is characterized in that the solid product
Amount ratio with acetone is 0.5g:100mL, and the temperature of elution is 60 DEG C, and the time of elution is for 24 hours.
8. the preparation method of double reaction channel photochemical catalysts according to claim 1, which is characterized in that the EDTA's is dense
Degree is 0.5g/L.
9. the preparation method of double reaction channel photochemical catalysts according to claim 1, which is characterized in that the vacuum drying
Temperature be 30 DEG C, time 12h.
10. being used for double reaction channel photochemical catalysts that any one of claim 1~9 preparation method obtains based on different anti-
Channel selectivity is answered to restore Cr6+And the purposes of synchronous photocatalytic degradation tetracycline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811515378.XA CN109589984B (en) | 2018-12-12 | 2018-12-12 | Preparation method and application of double-reaction-channel photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811515378.XA CN109589984B (en) | 2018-12-12 | 2018-12-12 | Preparation method and application of double-reaction-channel photocatalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109589984A true CN109589984A (en) | 2019-04-09 |
| CN109589984B CN109589984B (en) | 2021-11-23 |
Family
ID=65961714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811515378.XA Active CN109589984B (en) | 2018-12-12 | 2018-12-12 | Preparation method and application of double-reaction-channel photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109589984B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113578384A (en) * | 2021-08-19 | 2021-11-02 | 江苏大学 | Ectopic reaction Cr6+Preparation method and application of ion imprinting photocatalytic membrane |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945580A (en) * | 2015-07-16 | 2015-09-30 | 江苏大学 | Manufacturing method and application of Cr(VI) anion imprinted material |
| CN105664950A (en) * | 2016-01-04 | 2016-06-15 | 南京林业大学 | Preparation method of nano porous ZnFe2O4 |
| US20170092396A1 (en) * | 2014-05-20 | 2017-03-30 | Politecnico Di Milano | Amphiphilic magnetic nanoparticles and aggregates to remove hydrocarbons and metal ions and synthesis thereof |
| CN107029251A (en) * | 2015-07-15 | 2017-08-11 | 河北工程大学 | A kind of individual layer molybdenum disulfide-zinc ferrite nano composite material and its preparation method and application |
| CN107573468A (en) * | 2017-10-13 | 2018-01-12 | 天津工业大学 | A kind of core-shell type magnetic fluorescence sense microballoon of Cr VI anion trace |
| CN108855144A (en) * | 2018-06-13 | 2018-11-23 | 江苏大学 | A kind of Magnetic fractionation porous C d2+The preparation method and applications of trace photocatalytic nanometer reactor |
-
2018
- 2018-12-12 CN CN201811515378.XA patent/CN109589984B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170092396A1 (en) * | 2014-05-20 | 2017-03-30 | Politecnico Di Milano | Amphiphilic magnetic nanoparticles and aggregates to remove hydrocarbons and metal ions and synthesis thereof |
| CN107029251A (en) * | 2015-07-15 | 2017-08-11 | 河北工程大学 | A kind of individual layer molybdenum disulfide-zinc ferrite nano composite material and its preparation method and application |
| CN104945580A (en) * | 2015-07-16 | 2015-09-30 | 江苏大学 | Manufacturing method and application of Cr(VI) anion imprinted material |
| CN105664950A (en) * | 2016-01-04 | 2016-06-15 | 南京林业大学 | Preparation method of nano porous ZnFe2O4 |
| CN107573468A (en) * | 2017-10-13 | 2018-01-12 | 天津工业大学 | A kind of core-shell type magnetic fluorescence sense microballoon of Cr VI anion trace |
| CN108855144A (en) * | 2018-06-13 | 2018-11-23 | 江苏大学 | A kind of Magnetic fractionation porous C d2+The preparation method and applications of trace photocatalytic nanometer reactor |
Non-Patent Citations (2)
| Title |
|---|
| 逯子扬等: "Z 型印迹ZnFe2O4/Ag/PEDOT 复合光催化剂的微波法合成及其选择性光催化四环素的性能和机理研究", 《第十一届全国环境催化与环境材料学术会议》 * |
| 金征宇等: "《基因与纳米探针——医学分子成像理论与实践》", 30 November 2017 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113578384A (en) * | 2021-08-19 | 2021-11-02 | 江苏大学 | Ectopic reaction Cr6+Preparation method and application of ion imprinting photocatalytic membrane |
| CN113578384B (en) * | 2021-08-19 | 2023-07-18 | 江苏大学 | Ectopic reaction Cr 6+ Preparation method and application of ion imprinting photocatalytic film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109589984B (en) | 2021-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cheng et al. | Efficient degradation of sulfamethazine in simulated and real wastewater at slightly basic pH values using Co-SAM-SCS/H2O2 Fenton-like system | |
| You et al. | Magnetic cobalt ferrite biochar composite as peroxymonosulfate activator for removal of lomefloxacin hydrochloride | |
| Chen et al. | Degradation of tartrazine by peroxymonosulfate through magnetic Fe2O3/Mn2O3 composites activation | |
| Quan et al. | Simulated photocatalytic aging of biochar in soil ecosystem: Insight into organic carbon release, surface physicochemical properties and cadmium sorption | |
| Anirudhan et al. | Adsorption of chromium (VI) from aqueous solutions by glycidylmethacrylate-grafted-densified cellulose with quaternary ammonium groups | |
| Hou et al. | Chitosan/hydroxyapatite/Fe3O4 magnetic composite for metal-complex dye AY220 removal: recyclable metal-promoted Fenton-like degradation | |
| Lazaridis et al. | Sorptive removal of trivalent and hexavalent chromium from binary aqueous solutions by composite alginate–goethite beads | |
| Li et al. | Synthesis of ion-imprinted chitosan-TiO2 adsorbent and its multi-functional performances | |
| Abbasi et al. | Synthesis of grass-like structured Mn-Fe layered double hydroxides/PES composite adsorptive membrane for removal of malachite green | |
| US20200048117A1 (en) | Method for removing hexavalent chromium from water bodies by sodium oxalate-modified zero-valent iron | |
| CN103934034A (en) | Preparation method of loading iron based metal organic skeleton out phase Fenton catalyst and application thereof | |
| CN101961662B (en) | Method for preparing ion imprinting supported composite photocatalyst | |
| Rajeswari et al. | Cellulose acetate based biopolymeric mixed matrix membranes with various nanoparticles for environmental remediation-A comparative study | |
| CN105728041B (en) | A kind of preparation method of the PPy@ZnFe2O4 magnetic blotting composite photo-catalysts of the single-minded identification of selectivity | |
| CN105566400B (en) | Heterogeneous cobalt metal-organic framework and preparation and the application in field of waste water treatment | |
| CN103769058A (en) | Preparation method of carbonized chitosan adsorbent, adsorbent and application method of absorbent | |
| Wu et al. | The removal of tetracycline, oxytetracycline, and chlortetracycline by manganese oxide–doped copper oxide: the behaviors and insights of Cu-Mn combination for enhancing antibiotics removal | |
| Yang et al. | Preparation of activated carbon from waste cation exchange resin and its application in wastewater treatment | |
| CN109928510A (en) | A kind of Schwertmannite preparation method based on ZVI reduction coupling microorganism | |
| CN109206554B (en) | Ion imprinted polymer material for photo-reduction of hexavalent chromium and preparation and application thereof | |
| Yazid et al. | Removal of congo red from aqueous solution using cuttlefish bone powder | |
| Guo et al. | Fabrication of a novel separation-free heterostructured photocatalyst with enhanced visible light activity in photocatalytic degradation of antibiotics | |
| CN113042105B (en) | Preparation method of hydroxyapatite nanowire combined cobalt MOFs beaded catalyst | |
| CN109589984A (en) | A kind of preparation method and applications of double reaction channel photochemical catalysts | |
| D'Souza et al. | Green carbon induced super hydrophilic bioFoam filters for hazardous emerging pollutants removal and their sustainable value addition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |