CN110368919A - A kind of nano-stick array thin film type photochemical catalyst and application thereof - Google Patents
A kind of nano-stick array thin film type photochemical catalyst and application thereof Download PDFInfo
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- CN110368919A CN110368919A CN201910529266.8A CN201910529266A CN110368919A CN 110368919 A CN110368919 A CN 110368919A CN 201910529266 A CN201910529266 A CN 201910529266A CN 110368919 A CN110368919 A CN 110368919A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 239000010409 thin film Substances 0.000 title claims abstract description 20
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 claims abstract description 49
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000008367 deionised water Substances 0.000 claims abstract description 25
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000002351 wastewater Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 19
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims abstract description 8
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract 2
- 239000010408 film Substances 0.000 claims description 34
- 101150073096 NRAS gene Proteins 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 238000005352 clarification Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 210000000232 gallbladder Anatomy 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 13
- 238000005286 illumination Methods 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910003264 NiFe2O4 Inorganic materials 0.000 description 2
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000011953 bioanalysis Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000002699 waste material 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
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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
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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
- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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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Abstract
The present invention discloses a kind of nano-stick array thin film type photochemical catalyst, it takes following method to be prepared: one, substrate being made with Fluorin doped stannic oxide (FTO) electro-conductive glass, it is put into autoclave polytetrafluoroethylliner liner, body liquid before reaction that deionized water, butyl titanate mix is poured into liner, it is put into autoclave and is increased in the baking ovens of 150 DEG C of temperature and react, take out cooling, rinsing, room temperature is dried: two, stoichiometrically 2:0.5:0.5 prepares Fe (NO3)3、NiNO3With Zn (NO3)2Mixed solution, the TiO that will be prepared2NRAs is thin film dipped in mixed liquor, and taking-up is dried is calcined with Muffle furnace again, obtains catalyst TiO2NRAs/Ni0.5Zn0.5Fe2O4；Application of the catalyst of the present invention in processing waste water containing uns-dimethylhydrazine.Catalyst of the present invention have the advantages that efficiently, energy conservation, it is recyclable recycle, operating cost is low etc..
Description
Technical field
The present invention relates to Wastewater Pollutant process field, specifically a kind of nano-stick array thin film type photochemical catalyst and
Its purposes.
Background technique
Uns-dimethylhydrazine (UDMH) has the characteristic of high specific impulse, is widely used as the liquid of missile armament, satellite launcher
Propellant.With the fast development of China's military field and civil aerospace technology cause, a large amount of uns-dimethylhydrazine, which comes into operation, to be kept away
That exempts from causes serious environmental pollution problem, especially containing the waste water of uns-dimethylhydrazine, not to the threat of environment and human health
It can despise, cause relevant department to pay much attention to the improvement of uns-dimethylhydrazine sewage.
Currently, the processing for the waste water containing UDMH is broadly divided into physical method, bioanalysis and chemical method.Wherein, physical method master
UDMH molecule in water is separated using principles such as absorption, but generally existing processing capacity is lower and subsequent needs secondary treatment
Problem；Bioanalysis is mainly using active microorganism or water plant etc. to UDMH molecule progress degradation treatment in water body, but by
It is harsh in the survival condition of organism, the easy in inactivation when handling the waste water containing UDMH, and research shows that Biochemical method ability compared with
Low, the period is longer；Chemical method mainly handles UDMH molecule in water, but generally existing energy consumption using oxidation or reduction process
The problem of larger, higher cost, and the salts substances such as Cu, Fe, Co being added are difficult to recycle, and be easy to cause secondary pollution of water
The problem of.
Summary of the invention
The purpose of the present invention is in order to solve the above technical problems, current inventor provides a kind of nano-stick array thin film types to urge
Agent and application thereof；
The technical scheme is that a kind of nano-stick array thin film type catalyst, takes following method to be prepared:
Step 1: hydro-thermal reaction method prepares TiO2Nanometer stick array (NRAs) film；
Make substrate with Fluorin doped stannic oxide (FTO) electro-conductive glass, size of foundation base is l.5cm × 3cm.The precursor liquid of reaction
It is mixed by 10ml concentrated hydrochloric acid (36.8%), 10ml deionized water, 0.4ml butyl titanate, first by 10ml concentrated hydrochloric acid
(36.8%) and 10ml deionized water mixes and magnetic agitation is uniform, and metatitanic acid fourth is then added dropwise in the case where being stirred continuously
Ester solution continues to stir above-mentioned mixed solution to transparent clarification, and the precursor liquid as hydro-thermal reaction is spare.
The substrate cleaned up is put into the polytetrafluoroethylliner liner of the autoclave of 50ml, keeps base conductive face
Downward, and by one side it leans against on the gallbladder wall of liner.Body liquid before above-mentioned hydro-thermal reaction is poured into liner again, and liner is put
Enter in autoclave shell, tightens.Finally this autoclave is put into the baking oven for being increased to 150 DEG C of temperature and is reacted
5h after reaction cools down autoclave taking-up at room temperature, takes out sample and with a large amount of deionized water rinsed clean, room
It is dried under temperature spare.
Step 2: preparing TiO using immersion deposition calcination method2 NRAs/Ni0.5Zn0.5Fe2O4Film.First based on chemistry
Amount prepares Fe (NO than 2:0.5:0.53)3、NiNO3With Zn (NO3)2Mixed solution, wherein Fe (NO3)3Concentration is 0.25mol/L,
NiNO3With Zn (NO3)2Concentration is 0.0625mol/L.Then the TiO that will be prepared2NRAs is thin film dipped above-mentioned in 10-20ml
0.5-1.5h in mixed liquor takes out film and impregnates 4-6s in deionized water.Obtained film is at room temperature after natural drying
Again with Muffle furnace with 500 DEG C of temperature calcination 1.5-2.5h, when calcining, heats up and the speed of cooling is maintained at 4-6 DEG C/min, after
Obtain catalyst TiO2 NRAs/Ni0.5Zn0.5Fe2O4。
Further, hydro-thermal reaction method prepares TiO in the aforementioned first step2NRAs film can use indium doping stannic oxide
(ITO) electro-conductive glass makees substrate.
Further, in aforementioned second step, the TiO that will prepare2NRAs is thin film dipped in the above-mentioned mixed liquor of 15ml
1h takes out film and impregnates 5s in deionized water.Obtained film is at room temperature after natural drying again with Muffle furnace with 500 DEG C
Temperature calcination 2h, heat up when calcining and the speed of cooling be maintained at 5 DEG C/min, after obtain catalyst TiO2 NRAs/
Ni0.5Zn0.5Fe2O4。
Further, a kind of purposes of nano-stick array thin film type catalyst of the present invention is containing uns-dimethylhydrazine for handling
Application in waste water.
The wastewater treatment containing uns-dimethylhydrazine is carried out using catalyst of the invention, it is not only high-efficient, but also handle very thorough
Bottom can remove 99% or more uns-dimethylhydrazine, be a kind of efficient, energy saving, easy to operate, catalyst can be recycled recycle,
The low water treatment technology of operating cost.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this hair
Bright further description.
Embodiment 1
A kind of nano-stick array thin film type catalyst, takes following method to be prepared:
Step 1: hydro-thermal reaction method prepares TiO2NRAs film.
Make substrate with Fluorin doped stannic oxide (FTO) electro-conductive glass, size of foundation base is l.5cm × 3cm.The precursor liquid of reaction
It is mixed by 10ml concentrated hydrochloric acid (36.8%), 10ml deionized water, 0.4ml butyl titanate, first by 10ml concentrated hydrochloric acid
(36.8%) and 10ml deionized water mixes and magnetic agitation is uniform, and metatitanic acid fourth is then added dropwise in the case where being stirred continuously
Ester solution continues to stir above-mentioned mixed solution to transparent clarification, and the precursor liquid as hydro-thermal reaction is spare.
The substrate cleaned up is put into the polytetrafluoroethylliner liner of the autoclave of 50ml, keeps base conductive face
Downward, and by one side it leans against on the gallbladder wall of liner.Body liquid before above-mentioned hydro-thermal reaction is poured into liner again, and liner is put
Enter in autoclave shell, tightens.Finally this autoclave is put into the baking oven for being increased to 150 DEG C of temperature and is reacted
5h after reaction cools down autoclave taking-up at room temperature, takes out sample and with a large amount of deionized water rinsed clean, room
It is dried under temperature spare.
Step 2: preparing TiO using immersion deposition calcination method2 NRAs/Ni0.5Zn0.5Fe2O4Film.First based on chemistry
Amount prepares Fe (NO than 2:0.5:0.53)3、NiNO3With Zn (NO3)2Mixed solution, wherein Fe (NO3)3Concentration is 0.25mol/L,
NiNO3With Zn (NO3)2Concentration is 0.0625mol/L.Then the TiO that will be prepared2NRAs is thin film dipped in the above-mentioned mixing of 10ml
1.5h in liquid takes out film and impregnates 6s in deionized water.Obtained film uses Muffle furnace again after natural drying at room temperature
Heat up with 500 DEG C of temperature calcination 2.5h, when calcining and the speed of cooling all keep 4 DEG C/min, after obtain catalyst TiO2
NRAs/Ni0.5Zn0.5Fe2O4。
Embodiment 2
Step 1: hydro-thermal reaction method prepares TiO2NRAs film.
Make substrate with indium doping stannic oxide (ITO) electro-conductive glass, size of foundation base is l.5cm × 3cm.The precursor liquid of reaction
It is mixed by 10ml concentrated hydrochloric acid (36.8%), 10ml deionized water, 0.4ml butyl titanate, first by 10ml concentrated hydrochloric acid
(36.8%) and 10ml deionized water mixes and magnetic agitation is uniform, and metatitanic acid fourth is then added dropwise in the case where being stirred continuously
Ester solution continues to stir above-mentioned mixed solution to transparent clarification, and the precursor liquid as hydro-thermal reaction is spare.
The substrate cleaned up is put into the polytetrafluoroethylliner liner of the autoclave of 50ml, keeps base conductive face
Downward, and by one side it leans against on the gallbladder wall of liner.Body liquid before above-mentioned hydro-thermal reaction is poured into liner again, and liner is put
Enter in autoclave shell, tightens.Finally this autoclave is put into the baking oven for being increased to 150 DEG C of temperature and is reacted
5h after reaction cools down autoclave taking-up at room temperature, takes out sample and with a large amount of deionized water rinsed clean, room
It is dried under temperature spare.
Step 2: preparing TiO using immersion deposition calcination method2 NRAs/Ni0.5Zn0.5Fe2O4Film.First based on chemistry
Amount prepares Fe (NO than 2:0.5:0.53)3、NiNO3With Zn (NO3)2Mixed solution, wherein Fe (NO3)3Concentration is 0.25mol/L,
NiNO3With Zn (NO3)2Concentration is 0.0625mol/L.Then the TiO that will be prepared2NRAs is thin film dipped in the above-mentioned mixing of 20ml
0.5h in liquid takes out film and impregnates 4s in deionized water.Obtained film uses Muffle furnace again after natural drying at room temperature
Heat up with 500 DEG C of temperature calcination 1.5h, when calcining and the speed of cooling all keep 6 DEG C/min, after obtain catalyst TiO2
NRAs/Ni0.5Zn0.5Fe2O4。
Embodiment 3
Step 1: hydro-thermal reaction method prepares TiO2NRAs film.
Make substrate with Fluorin doped stannic oxide (FTO) electro-conductive glass, size of foundation base is l.5cm × 3cm.The precursor liquid of reaction
It is mixed by 10ml concentrated hydrochloric acid (36.8%), 10ml deionized water, 0.4ml butyl titanate, first by 10ml concentrated hydrochloric acid
(36.8%) and 10ml deionized water mixes and magnetic agitation is uniform, and metatitanic acid fourth is then added dropwise in the case where being stirred continuously
Ester solution continues to stir above-mentioned mixed solution to transparent clarification, and the precursor liquid as hydro-thermal reaction is spare.
The substrate cleaned up is put into the polytetrafluoroethylliner liner of the autoclave of 50ml, keeps base conductive face
Downward, and by one side it leans against on the gallbladder wall of liner.Body liquid before above-mentioned hydro-thermal reaction is poured into liner again, and liner is put
Enter in autoclave shell, tightens.Finally this autoclave is put into the baking oven for being increased to 150 DEG C of temperature and is reacted
5h after reaction cools down autoclave taking-up at room temperature, takes out sample and with a large amount of deionized water rinsed clean, room
It is dried under temperature spare.
Step 2: preparing TiO using immersion deposition calcination method2 NRAs/Ni0.5Zn0.5Fe2O4Film.First based on chemistry
Amount prepares Fe (NO than 2:0.5:0.53)3、NiNO3With Zn (NO3)2Mixed solution, wherein Fe (NO3)3Concentration is 0.25mol/L,
NiNO3With Zn (NO3)2Concentration is 0.0625mol/L.Then the TiO that will be prepared2NRAs is thin film dipped in the above-mentioned mixing of 15ml
1h in liquid takes out film and impregnates 5s in deionized water.Obtained film at room temperature after natural drying again with Muffle furnace with
500 DEG C of temperature calcination 2h, heats up when calcining and the speed of cooling all keeps 5 DEG C/min, after obtain catalyst TiO2 NRAs/
Ni0.5Zn0.5Fe2O4。
Comparative experiments example
With a kind of TiO prepared in embodiment 32 NRAs/Ni0.5Zn0.5Fe2O4Film is as photochemical catalyst, under light illumination
It degrades to uns-dimethylhydrazine in waste water.Light source used in the photocatalytic degradation process of waste water containing UDMH is provided by xenon lamp, light source
Exposure intensity is measured by strong light light power meter.
By the TiO of preparation2 NRAs/Ni0.5Zn0.5Fe2O4Film (effective area 6cm2) it is put into the burning that volume is 100ml
In cup (one side with film is upward), then by waste water containing UDMH that 15ml concentration is 20mg/L (by deionized water and pure
UDMH solution is formulated) pour into above-mentioned beaker.Before light-catalyzed reaction starts, dark adsorption 30min first, so that catalyst pair
UDMH molecule reaches absorption and desorption equilibrium.After dark adsorption, opens light source and carry out photocatalytic degradation reaction, timing sampling
Measure remaining UDMH content in waste water.Entire light-catalyzed reaction process is carried out in recirculated cooling water (4 DEG C), to prevent
Waste water evaporates by heat because of illumination.
Experimental example 4: taking the above-mentioned 15ml concentration containing photochemical catalyst of the present invention prepared is the waste water containing UDMH of 20mg/L,
It is 60mW/cm in intensity of illumination2The lower 180min that degrades of visible light (λ >=420nm) irradiation, the degradation rate of UDMH can reach 32%
Left and right.Under equal conditions, the TiO of similar approach preparation2 NRAs/NiFe2O4And TiO2 NRAs/ZnFe2O4Degradation to UDMH
Rate is only 21.06% and 14.19%；
Conclusion: photochemical catalyst TiO of the invention2 NRAs/Ni0.5Zn0.5Fe2O4To the degradation rate of UDMH than similar approach system
Standby photochemical catalyst TiO2 NRAs/NiFe2O4And TiO2 NRAs/ZnFe2O4Degradation rate will be higher by least 10% or so.
Experimental example 5: taking the above-mentioned 15ml concentration containing photochemical catalyst of the present invention prepared is the waste water containing UDMH of 20mg/L,
It is 60mW/cm in intensity of illumination2The lower 180min that degrades of simulated solar irradiation irradiation, the degradation rate of UDMH can reach 47% or so.
Experimental example 6: the intensity of illumination in embodiment 5 is adjusted to 120mW/cm2, UDMH in the identical situation of other conditions
Degradation rate can reach 86% or so.Continue the intensity of illumination in embodiment 5 being adjusted to 180mW/cm2, the degradation rate of UDMH
It can reach 99% or more.
Experimental example 7: UDMH initial concentration in 5 waste water of embodiment is improved to 40mg/L, in the identical situation of other conditions
The degradation rate of UDMH is 36% or so, total concentration reduction amount △ C=(C0-Ct)/C0(C0For UDMH initial concentration, C in solutiontFor
UDMH concentration in solution when the reaction progress time is t) it is about 14.4mg/L, the △ C of UDMH is about under the same terms in embodiment 1
9.4mg/L.Continue to improve UDMH initial concentration in 4 waste water of embodiment to 60mg/L, UDMH in the identical situation of other conditions
Degradation rate be 25% or so, △ C be about 15mg/L.Under same reaction conditions, UDMH initial concentration in waste water is continued to lift up,
The continuous reduction of UDMH degradation rate, but △ C increase is unobvious.Thus obtain: the appropriate initial concentration for increasing UDMH can make multiple
The photocatalytic degradation capability for closing film is not fully exerted, and avoids the waste of resource, has one to the engineer application of wastewater treatment
Fixed directive significance.
Experimental example 8: the citric acid of 1mmol/L is added in the waste water containing UDMH of experimental example 5,6,7, will lead to the drop of UDMH
The decline of solution rate；And the blowing air in the waste water containing UDMH of embodiment 5,6,7, then facilitate the fast degradation of UDMH.Thus it obtains:
Pass through the degradation speed of UDMH in the adjustable reaction process of addition of additive.
Experimental example 9: the photochemical catalyst in experimental example 5 is washed with deionized water after drying and is reused, entirely degraded
Journey carries out 5 times again according to experimental example 5, and the degradation rate of UDMH is always held at 32% or so, and stability is up to 99%.Applicant's system
It is standby to cross TiO2NRAs/CdS film photocatalyst, wherein TiO2The preparation method and TiO of NRAs2 NRAs/Ni0.5Zn0.5Fe2O4
Middle TiO2NRAs is identical, TiO2NRAs/CdS film is about to the degradation rate of uns-dimethylhydrazine under 4 equal conditions of embodiment
36.77%, but it is reused rear stability three times and drops to 22.63% than that, and stability is only 58.7%.Thus may be used
See, compared with the photochemical catalysts such as CdS, CuS, TiO2 NRAs/Ni0.5Zn0.5Fe2O4To UDMH wastewater photocatalytic degradation ability phase
Under the premise of difference is very few, stability is higher, improves the recycling efficiency of photochemical catalyst, and can avoid toxic metal ions anti-
It should be discharged into water body in the process and cause secondary pollution.
From the above comparative experiments, it can be concluded that, photocatalyst for degrading effect prepared by the present invention is best！
A kind of nanometer stick array (NRAs) film prepared using the present embodiment 1,2 methods is as photochemical catalyst in same item
Under part, available essentially identical effect.
A kind of nanometer stick array (NRAs) film of the invention also has the advantage that
(1) compared with the method for the processing uns-dimethylhydrazine waste water such as hydrogen peroxide oxidation, ultraviolet irradiation, ozone oxidation, the light
Catalytic treatment uns-dimethylhydrazine waste water system can make full use of solar energy, facilitate the reduction of wastewater treatment energy consumption, saving processing
Cost.
(2) compared with powder type photochemical catalyst, the TiO2 NRAs/Ni0.5Zn0.5Fe2O4Film-type photochemical catalyst be easy to from
Recycling and reusing in water body.
(3) compared with the photochemical catalysts such as CdS, CuS, the TiO2 NRAs/Ni0.5Zn0.5Fe2O4Film-type photochemical catalyst is stablized
Property it is higher, can avoid because toxic metal ions reaction process punching be discharged into water body due to cause secondary pollution, can recycle.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (4)
1. a kind of nano-stick array thin film type catalyst, which is characterized in that following method is taken to be prepared: step 1: hydro-thermal
Reaction method prepares TiO2Nanometer stick array (NRAs) film:
Make substrate with Fluorin doped stannic oxide (FTO) electro-conductive glass, size of foundation base is l.5cm × 3cm.The precursor liquid of reaction by
10ml concentrated hydrochloric acid (36.8%), 10ml deionized water, 0.4ml butyl titanate mix, first by 10ml concentrated hydrochloric acid
(36.8%) and 10ml deionized water mixes and magnetic agitation is uniform, and metatitanic acid fourth is then added dropwise in the case where being stirred continuously
Ester solution continues to stir above-mentioned mixed solution to transparent clarification, and the precursor liquid as hydro-thermal reaction is spare.
The substrate cleaned up is put into the polytetrafluoroethylliner liner of the autoclave of 50ml, base conductive is kept to face
Under, and one side is leant against on the gallbladder wall of liner.Body liquid before above-mentioned hydro-thermal reaction is poured into liner again, and liner is put into
In autoclave shell, tighten.Finally this autoclave is put into the baking oven for being increased to 150 DEG C of temperature and reacts 5h,
Autoclave taking-up is cooled down at room temperature after reaction, takes out sample and with a large amount of deionized water rinsed clean, room temperature
Under dry it is spare.
Step 2: preparing TiO using immersion deposition calcination method2 NRAs/Ni0.5Zn0.5Fe2O4Film.First stoichiometrically
2:0.5:0.5 prepares Fe (NO3)3、NiNO3With Zn (NO3)2Mixed solution, wherein Fe (NO3)3Concentration is 0.25mol/L, NiNO3
With Zn (NO3)2Concentration is 0.0625mol/L.Then the TiO that will be prepared2NRAs is thin film dipped in the above-mentioned mixed liquor of 10-20ml
Middle 0.5-1.5h takes out film and impregnates 4-6s in deionized water.Obtained film uses horse again after natural drying at room temperature
Not furnace is with 500 DEG C of temperature calcination 1.5-2.5h, and when calcining heats up and the speed of cooling is maintained at 4-6 DEG C/min, after urged
Agent TiO2 NRAs/Ni0.5Zn0.5Fe2O4。
2. a kind of nano-stick array thin film type catalyst according to claim 1, which is characterized in that water in the first step
Thermal response method prepares TiO2 NRAs film and makees substrate with indium doping stannic oxide (ITO) electro-conductive glass.
3. a kind of nano-stick array thin film type catalyst according to claim 1, which is characterized in that in the second step,
The TiO that will be prepared2The thin film dipped 1h in the above-mentioned mixed liquor of 15ml of NRAs takes out film and impregnates 5s in deionized water.
Obtained film is at room temperature after natural drying again with Muffle furnace with 500 DEG C of temperature calcination 2h, and when calcining heats up and cooling
Speed is maintained at 5 DEG C/min, after obtain catalyst TiO2 NRAs/Ni0.5Zn0.5Fe2O4。
4. a kind of purposes of nano-stick array thin film type catalyst, which is characterized in that the application in waste water containing uns-dimethylhydrazine.
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Application publication date: 20191025 |