CN106560230A - Application of composite catalyst based on iron-and-nitrogen-codoped titanium dioxide to photocatalysis of nitric oxide - Google Patents
Application of composite catalyst based on iron-and-nitrogen-codoped titanium dioxide to photocatalysis of nitric oxide Download PDFInfo
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- CN106560230A CN106560230A CN201610392666.5A CN201610392666A CN106560230A CN 106560230 A CN106560230 A CN 106560230A CN 201610392666 A CN201610392666 A CN 201610392666A CN 106560230 A CN106560230 A CN 106560230A
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- titanium dioxide
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- composite catalyst
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 19
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 57
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 47
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011941 photocatalyst Substances 0.000 claims abstract description 30
- 239000005011 phenolic resin Substances 0.000 claims abstract description 27
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004202 carbamide Substances 0.000 claims abstract description 24
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 69
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 51
- 239000011259 mixed solution Substances 0.000 claims description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 32
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 30
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 235000013877 carbamide Nutrition 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 229960004756 ethanol Drugs 0.000 claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- -1 Polyethylene Polymers 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000013081 microcrystal Substances 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- LCDFWRDNEPDQBV-UHFFFAOYSA-N formaldehyde;phenol;urea Chemical compound O=C.NC(N)=O.OC1=CC=CC=C1 LCDFWRDNEPDQBV-UHFFFAOYSA-N 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000003980 solgel method Methods 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003795 desorption Methods 0.000 abstract description 2
- 229920001568 phenolic resin Polymers 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 239000004721 Polyphenylene oxide Substances 0.000 abstract 1
- 229920000570 polyether Polymers 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229920000428 triblock copolymer Polymers 0.000 description 6
- 229920001807 Urea-formaldehyde Polymers 0.000 description 5
- 239000008098 formaldehyde solution Substances 0.000 description 5
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 229910011208 Ti—N Inorganic materials 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910002703 Al K Inorganic materials 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 238000003483 aging Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/804—UV light
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention discloses application of a composite catalyst based on iron-and-nitrogen-codoped titanium dioxide to photocatalysis of nitric oxide. The composite catalyst is prepared from a phenolic resin oligomer with dispersed butyl titanate, a mixture of liquid polyether and absolute ethyl alcohol, and a solution containing urea and ferric nitrate through one-shot sol-gel process. Nanometer titanium dioxide is uniformly distributed on the surface of mesoporous carbon, so a contact area of the composite catalyst and target pollutants is increased; iron-and-nitrogen-codoping improves the utilization rate of light and photocatalysis efficiency; and through the one-shot sol-gel process and roasting process, bonding between titanium dioxide and mesoporous carbon is realized, steps are simple and energy consumption is low; and under the condition that oxygen and water vapor participate, NO is converted into HNO3 and HNO2 through photocatalysis in the presence of ultraviolet-visible light, the converted HNO3 and HNO2 adhere onto the surface of the photocatalyst, and desorption the of above products and regeneration of the photocatalyst can be realized through washing and soaking.
Description
Technical field
The invention belongs to photocatalysis technology field, more specifically, be related to a kind of ferrum nitrogen-doped titanium dioxide with it is hollow
Composite photo-catalyst of carbon and preparation method thereof.
Background technology
Anatase titanium dioxide can photocatalytic pollutant degradation, and have low energy consumption, non-secondary pollution the features such as,
Extensively apply in the fields such as purification of air, wastewater treatment.But titanium dioxide has higher energy gap, can only be shorter by wavelength
Ultraviolet excitation, (about 3%-5%) low to sun light utilization efficiency.Secondly, photohole is combined to easy with electronics so that dioxy
The photocatalysis efficiency for changing titanium is relatively low.3rd, it is at present to adopt Study on Synthesis of Nanocrystal Titanium Dionide powder more, using
Need to support in journey.The contact area of nano titanium oxide and target contaminant, is equally to affect titanium dioxide optical catalyst profit
With the key factor of rate.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of ferrum nitrogen-doped titanium dioxide and hollow carbon
Composite photo-catalyst and preparation method thereof, by the preparation process of ferrum nitrogen-doped titanium dioxide and the organic knot of mesoporous carbon forming process
Close, using a sol-gel process, synchronously prepare titanium dioxide and mesoporous carbon materials, this forming process makes titanium dioxide
Effectively it is crosslinked with carbon structure, titanium dioxide is evenly distributed in carbon structure, and a collosol and gel and roasting process, simplify
Preparation process, reduces energy consumption.
The technical purpose of the present invention is achieved by following technical proposals:
Composite photo-catalyst of ferrum nitrogen-doped titanium dioxide and hollow carbon and preparation method thereof, is carried out as steps described below:
Step 1, by the first mixed solution and the second mixed solution mix homogeneously, then the 3rd mixed solution of Deca thereto,
State is kept stirring for during Deca and is persistently stirred after completion of dropwise addition, until forming (transparent) colloidal sol;
Step 2, the vitreosol that step 1 is obtained are aged 8-12 hours under 20-25 degrees Celsius of room temperature, by what is obtained
Gel is placed in 100-110 DEG C and is dried 8-10h, gives full play to the ethanol and moisture that residue in gel, and xeraphium is obtained
End;
Step 3, dried powder prepared by step 2 in a nitrogen atmosphere, with the programming rate of 1-2 DEG C/min from room temperature
20-25 degrees Celsius are warming up to 800-850 DEG C, and the insulation under 800-850 degrees Celsius carries out calcining 2-4h, obtains ferrum N doping two
The composite photo-catalyst of titanium oxide and hollow carbon.
In above-mentioned technical proposal, the 300-400m of specific surface area of composite photo-catalyst2/ g, preferably 320-350m2/g。
In above-mentioned technical proposal, the pore-size distribution of composite photo-catalyst belongs to mesoporous channels in 3-4.5nm, is conducive to
The diffusion of contaminant molecule and product molecule.
In the composite photo-catalyst of the present invention, nitrogen source, the addition of source of iron change the combination energy peak position of Ti and O, explanation
Two kinds of ions have effectively entered TiO2Lattice net, and substantially increase in visible region absorption spectrum after adulterating.
In above-mentioned technical proposal, in step 3,820-840 degrees Celsius are warming up to, 2.5-3.5 hours are calcined.
In above-mentioned technical proposal, in step 2, digestion time is 10-12 hours.
When in above-mentioned technical proposal, in step 1, by the first mixed solution and the second mixed solution mix homogeneously, choosing
100-200 turns of mechanical agitation/min is selected, mixing time is 15-25min.
In above-mentioned technical proposal, in step 1, state is kept stirring for during Deca and is continued after completion of dropwise addition
20-40min is persistently stirred in stirring, 100-200 turns of mechanical agitation/min after completion of dropwise addition.
In above-mentioned technical proposal, in step 1, Deca process is using at the uniform velocity Deca, 10-30min of Deca used time.
In above-mentioned technical proposal, in step 1, the first mixed solution is prepared as steps described below:
Step 1,20-30 mass parts phenol is melted at 40 DEG C, is added dropwise over 45-55 mass parts quality percentages thereto
Number is the NaOH aqueous solutions (quality sum of sodium hydroxide quality/sodium hydroxide and water) of 20wt%, is then added dropwise over 40-45
Mass parts mass percent is 37% formalin (quality sum of formaldehyde quality/formaldehyde and water), by the mixing for obtaining
Liquid 100-150 turns at 70 DEG C/mixing speed of min stirring 1-2h, be cooled to 20-25 degrees Celsius of room temperature, use 0.5mol/L
The aqueous solution of HCl mixed liquor pH value is adjusted to into 7.0, then mixed liquor is dried in Rotary Evaporators, obtains phenolic resin low
Polymers;In Deca, 3-5ml per minute is controlled;
Step 2, adds dehydrated alcohol to phenol resin oligomer prepared by step 1, is configured to phenol resin oligomer
Phenol resin solution (phenol resin oligomer quality/phenol resin oligomer and dehydrated alcohol of the mass percent for 10-20%
Quality sum), in phenol resin solution add 20-35 parts by volume butyl titanate, stir, obtain the first mixing molten
Liquid.
In above-mentioned technical proposal, in step 1, the second mixed solution is prepared as steps described below:
By the polyoxyethylene-poly-oxypropylene polyoxyethylene copolymer (CAS numberings are 106392-12-5) of 1-3 mass parts
Mix and be uniformly dispersed with the dehydrated alcohol of 15-25 mass parts, obtain the second mixed solution, due to mixing with dehydrated alcohol, gather
Oxygen ethylene-polyoxypropylene polyoxyethylene copolymer selects liquid form, can carry out molecular weight selection and city according to liquid form
Purchase, the preferably number-average molecular weight of the polyoxyethylene-poly-oxypropylene polyoxyethylene copolymer are 1000-2200.
In above-mentioned technical proposal, in step 1, the 3rd mixed solution is prepared as steps described below:
By 10-20 parts by volume dehydrated alcohol, 2-4 parts by volume distilled water, the mixing of 1-2 parts by volume aqueous solution of nitric acid, in nitric acid
In aqueous solution, the mass percent of nitric acid is 10-20%, is added to carbamide and ferric nitrate respectively as nitrogen source and source of iron,
It is (0.6-15) that carbamide adds quality with butyl titanate mass ratio:100, ferric nitrate adds quality and with butyl titanate mass ratio is
(0.6—15):100;Wherein carbamide addition quality and butyl titanate mass ratio are (1-5):100, ferric nitrate adds quality and titanium
Acid butyl ester mass ratio is (1-5):100.
In above-mentioned technical proposal, in step 1, the volume of the first mixed solution and the second mixed solution is consistent, is
1-2 times of 3rd mixed liquor volume.
XRD signs are carried out to the catalyst of the present invention, the use of instrument is Rigaku D/MAX2500 type X-ray diffractometers
(XRD), light source be CuK- α (λ=0.15418nm monochromators) ray, tube voltage 40kV, tube current 30mA, Scanning step
0.02 °, 3 °/min of sweep speed.The photocatalyst that test ferrum nitrogen-doped titanium dioxide is combined with mesoporous carbon, occurs significantly sharp
Titanium ore phase titanic oxide diffraction maximum, illustrates to have obtained the anatase titanium dioxide with photocatalysis performance;Occur in that graphite state
Carbon diffraction maximum, illustrate carbon with class graphite microcrystal as principal mode.
XPS signs are carried out to the catalyst of the present invention, the use of instrument is Perkin Elmer companies of U.S. PHI-1600 types X
X-ray photoelectron spectroscopy X instrument (XPS), Al K α anodes, 1486.6eV irradiation samples excite photoelectron, using dome-type precise electronic
Energy analyzer, it is fixed by energy pattern.It is 50eV that narrow spectrum scans through energy PE, and full scan passes through to be 187.85eV, with C
1s (284.6eV) is calibration standard.The photocatalyst that test ferrum nitrogen-doped titanium dioxide and mesoporous carbon are combined, detect C, Ti,
The presence of O, N and Fe element.By Fe2p spectral peaks, in the characteristic peak of 710.4eV, infer the Fe elements in sample and mainly deposited with+trivalent
.By N1s spectral peaks, in Ti-N the characteristic peak of N1s mainly in 398.8eV, O-Ti-N the characteristic peak of N1s near 400.4eV.
The catalyst sample of preparation shows characteristic peak near 398.8eV, 400.4eV, illustrates that elemental nitrogen doping enters TiO2Lattice.
By O1s spectral peaks, after doping iron, nitrogen, there is characteristic peak to the high energy direction 533.3eV that combines in O1s peaks, and illustrate in doping iron, nitrogen
Afterwards, increase a kind of oxygen of bonding state, it was demonstrated that the addition of two kinds of elements produces impact to the chemical state of oxygen, that is, remove elemental nitrogen pair
TiO2Lattice is doped into outside, and elemental iron enters TiO to a certain extent2Lattice.
Compared with prior art, the present invention propose a kind of photocatalyst that ferrum nitrogen-doped titanium dioxide is combined with mesoporous carbon and
Its preparation method, nano titanium oxide preparation process is combined with mesoporous carbon preparation process, in being distributed in nano titanium oxide
Hole carbon surface;And adulterate in titanium dioxide forming process nitrogen, iron ion, improve visible light-responded scope and photocatalysis efficiency.
Using a sol-gel process, titanium dioxide and mesoporous carbon materials are synchronously prepared, realize that titanium dioxide is effectively handed over carbon structure
Connection, makes titanium dioxide be evenly distributed in carbon structure, expands the contact area of photocatalyst and pollutant.While mesopore duct
Be conducive to the diffusion of contaminant molecule and product molecule, the final composite photo-catalyst specific surface area for preparing is average up to 300m2/
More than g.In titanium dioxide preparation process, nitrogen source and source of iron are added, makes nitrogen, iron ion effectively enter TiO2Lattice net, promotees
Enter photocatalyst to respond in visible-range, and improve photocatalysis efficiency.The present invention passes through a collosol and gel and roasting process,
Realize that ferrum nitrogen-doped titanium dioxide is compound with mesopore carbon structure simultaneously, simplify preparation process, reduce energy consumption.
Description of the drawings
Fig. 1 is the XRD spectra of catalyst of the present invention.
Fig. 2 is the XPS spectrum figure (1) of catalyst of the present invention.
Fig. 3 is the XPS spectrum figure (2) of catalyst of the present invention.
Fig. 4 is the XPS spectrum figure (3) of catalyst of the present invention.
Fig. 5 is the XPS spectrum figure (4) of catalyst of the present invention.
Fig. 6 is the absorbance comparison diagram of catalyst of the present invention and comparative catalyst.
Fig. 7 is the structural representation of the photocatalyst catalyzed conversion NO experimental systems used in the embodiment of the present invention.
Specific embodiment
Technical scheme is further illustrated with reference to specific embodiment.One base Industrial Co., Ltd. of commercial Shanghai
Polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO) F127, uses as triblock copolymer;Configuration nitric acid is water-soluble
Liquid, the mass percent of nitric acid is 20%;Configuration sodium hydrate aqueous solution, the mass percent of sodium hydroxide is 20%;Configuration
Formalin, the mass percent of formaldehyde is 37%.Stir in each step, mixing speed is stablized
100-120 turns/min.In technical solution of the present invention, each mass parts are 1g, and each parts by volume is 1mL, and first mixes molten
The consumption (by volume) of liquid, the second mixed solution and the 3rd mixed solution is consistent.Titanium dioxide powder is prepared using following methods
End, is tested as a comparison case:
(1) 8.5mL butyl titanates are mixed with 30mL dehydrated alcohol under room temperature, mechanical agitation 30min, obtains clarification molten
Liquid;
(2) 1.5mL tri-distilled waters, 15mL dehydrated alcohol and 1.0mL nitric acid are mixed, obtains solution;
(3) solution for preparing step 2 is slowly dropped in solution prepared by step 1 by dropper, is kept during Deca
Solution persistently stirs 30min in state is stirred vigorously after completion of dropwise addition, up to formation vitreosol, the Deca used time is
20min;
(4) colloidal sol is aged 10h at room temperature, then gained gel is placed in 105 DEG C of drying baker and is dried 4h, make residual
Ethanol and moisture evaporation in the gel totally, is obtained dried powder;
(5) powder is warming up to into 500 DEG C of insulations with 5 DEG C/min, calcines 2h, that is, obtain control sample titania powder.
When the preparation of catalyst of the present invention is carried out, the first mixed solution, the second mixed solution and are prepared first respectively
Three mixed solutions, then carry out solation, ageing, drying and calcination.
Embodiment 1
(1) 25g phenol is melted at 40 DEG C, is added dropwise over the NaOH aqueous solutions that 50g concentration is 20%, then dropwise added
Enter the formalin that 42g concentration is 37%.Mixed liquor stirs 1h at 70 DEG C, is cooled to room temperature, uses 0.5mol/L HCl solutions
Mixed liquor pH value is adjusted to into 7.0.Mixed liquor is dried in Rotary Evaporators, phenol resin oligomer is obtained.
(2) phenol resin oligomer obtained to step (1) adds dehydrated alcohol, is configured to the phenol that mass fraction is 15%
Urea formaldehyde solution.The butyl titanate of 25ml is added in phenol resin solution, is persistently stirred, is obtained dehydrated alcohol mixed solution (A
That is the first mixed solution).
(3) 2g triblock copolymers are mixed with 18g dehydrated alcohol, is stirred, (B i.e. second mixes to obtain ethanol solution
Close solution).
(4) by 15ml dehydrated alcohol, 3ml distilled water, the mixing of 1ml salpeter solutions;Using carbamide as nitrogen source, add in solution
Plus 5% (urea quality/butyl titanate quality) carbamide;Using ferric nitrate as source of iron, add 5% (nitric acid irony in solution
Amount/butyl titanate quality) ferric nitrate;Obtain mixed solution (C i.e. the 3rd mixed solution).
(5) solution (A) is mixed with solution (B), stirs 20min;Solution (C) is slowly dropped into by mixing by dropper subsequently
Solution, keeps solution in state is stirred vigorously, 30min is persistently stirred after completion of dropwise addition, until forming colloidal sol during Deca.
(6) colloidal sol is aged 8h at room temperature, then gained gel is placed in 105 DEG C of drying baker and is dried 8h, make residual
Ethanol and moisture evaporation in the gel totally, is obtained dried powder.
(7) by dried powder in a nitrogen atmosphere, 800 DEG C of insulations are to slowly warm up to 1 DEG C/min, calcine 2h, that is, obtain
The catalyst of the present invention.
Embodiment 2
(1) 20g phenol is melted at 40 DEG C, is added dropwise over the NaOH aqueous solutions that 45g concentration is 20%, then dropwise added
Enter the formalin that 40g concentration is 37%.Mixed liquor stirs 1h at 70 DEG C, is cooled to room temperature, uses 0.5mol/L HCl solutions
Mixed liquor pH value is adjusted to into 7.0.Mixed liquor is dried in Rotary Evaporators, phenol resin oligomer is obtained.
(2) phenol resin oligomer obtained to step (1) adds dehydrated alcohol, is configured to the phenol that mass fraction is 20%
Urea formaldehyde solution.The butyl titanate of 35ml is added in phenol resin solution, is persistently stirred, is obtained dehydrated alcohol mixed solution (A
That is the first mixed solution).
(3) 1g triblock copolymers are mixed with 25g dehydrated alcohol, is stirred, (B i.e. second mixes to obtain ethanol solution
Close solution).
(4) by 20ml dehydrated alcohol, 2ml distilled water, the mixing of 2ml salpeter solutions;Using carbamide as nitrogen source, add in solution
Plus 10% (urea quality/butyl titanate quality) carbamide;Using ferric nitrate as source of iron, add 10% (ferric nitrate in solution
Quality/butyl titanate quality) ferric nitrate;Obtain mixed solution (C i.e. the 3rd mixed solution).
(5) solution (A) is mixed with solution (B), stirs 15min;Solution (C) is slowly dropped into by mixing by dropper subsequently
Solution, keeps solution in state is stirred vigorously, 20min is persistently stirred after completion of dropwise addition, until forming colloidal sol during Deca.
(6) colloidal sol is aged 12h at room temperature, then gained gel is placed in 100 DEG C of drying baker and is dried 10h, made residual
Stay ethanol and moisture evaporation in gel totally, dried powder is obtained.
(7) by dried powder in a nitrogen atmosphere, 850 DEG C of insulations are to slowly warm up to 2 DEG C/min, calcine 4h, that is, obtain
The catalyst of the present invention.
Embodiment 3
(1) 30g phenol is melted at 40 DEG C, is added dropwise over the NaOH aqueous solutions that 50g concentration is 20%, then dropwise added
Enter the formalin that 40g concentration is 37%.Mixed liquor stirs 1h at 70 DEG C, is cooled to room temperature, uses 0.5mol/L HCl solutions
Mixed liquor pH value is adjusted to into 7.0.Mixed liquor is dried in Rotary Evaporators, phenol resin oligomer is obtained.
(2) phenol resin oligomer obtained to step (1) adds dehydrated alcohol, is configured to the phenol that mass fraction is 20%
Urea formaldehyde solution.The butyl titanate of 25ml is added in phenol resin solution, is persistently stirred, is obtained dehydrated alcohol mixed solution (A
That is the first mixed solution).
(3) 3g triblock copolymers are mixed with 15g dehydrated alcohol, is stirred, (B i.e. second mixes to obtain ethanol solution
Close solution).
(4) by 20ml dehydrated alcohol, 4ml distilled water, the mixing of 1ml salpeter solutions;Using carbamide as nitrogen source, add in solution
Plus 8% (urea quality/butyl titanate quality) carbamide;Using ferric nitrate as source of iron, add 10% (nitric acid irony in solution
Amount/butyl titanate quality) ferric nitrate;Obtain mixed solution (C i.e. the 3rd mixed solution).
(5) solution (A) is mixed with solution (B), stirs 20min;Solution (C) is slowly dropped into by mixing by dropper subsequently
Solution, keeps solution in state is stirred vigorously, 20min is persistently stirred after completion of dropwise addition, until forming colloidal sol during Deca.
(6) colloidal sol is aged 10h at room temperature, then gained gel is placed in 110 DEG C of drying baker and is dried 9h, make residual
Ethanol and moisture evaporation in the gel totally, is obtained dried powder.
(7) by dried powder in a nitrogen atmosphere, 820 DEG C of insulations are to slowly warm up to 1 DEG C/min, calcine 3h, that is, obtain
The catalyst of the present invention.
Embodiment 4
(1) 30g phenol is melted at 40 DEG C, is added dropwise over the NaOH aqueous solutions that 55g concentration is 20%, then dropwise added
Enter the formalin that 40g concentration is 37%.Mixed liquor stirs 1h at 70 DEG C, is cooled to room temperature, uses 0.5mol/L HCl solutions
Mixed liquor pH value is adjusted to into 7.0.Mixed liquor is dried in Rotary Evaporators, phenol resin oligomer is obtained.
(2) phenol resin oligomer obtained to step (1) adds dehydrated alcohol, is configured to the phenol that mass fraction is 20%
Urea formaldehyde solution.The butyl titanate of 35ml is added in phenol resin solution, is persistently stirred, is obtained dehydrated alcohol mixed solution (A
That is the first mixed solution).
(3) 1g triblock copolymers are mixed with 15g dehydrated alcohol, is stirred, (B i.e. second mixes to obtain ethanol solution
Close solution).
(4) by 20ml dehydrated alcohol, 3ml distilled water, the mixing of 2ml salpeter solutions;Using carbamide as nitrogen source, add in solution
Plus 0.6% (urea quality/butyl titanate quality) carbamide;Using ferric nitrate as source of iron, add 0.4% (nitric acid in solution
Weight of iron/butyl titanate quality) ferric nitrate;Obtain mixed solution (C i.e. the 3rd mixed solution).
(5) solution (A) is mixed with solution (B), stirs 15min;Solution (C) is slowly dropped into by mixing by dropper subsequently
Solution, keeps solution in state is stirred vigorously, 30min is persistently stirred after completion of dropwise addition, until forming colloidal sol during Deca.
(6) colloidal sol is aged 12h at room temperature, then gained gel is placed in 110 DEG C of drying baker and is dried 8h, make residual
Ethanol and moisture evaporation in the gel totally, is obtained dried powder.
(7) by dried powder in a nitrogen atmosphere, 830 DEG C of insulations are to slowly warm up to 2 DEG C/min, calcine 2h, that is, obtain
The catalyst of the present invention.
Embodiment 5
(1) 30g phenol is melted at 40 DEG C, is added dropwise over the NaOH aqueous solutions that 45g concentration is 20%, then dropwise added
Enter the formalin that 40g concentration is 37%.Mixed liquor stirs 1h at 70 DEG C, is cooled to room temperature, uses 0.5mol/L HCl solutions
Mixed liquor pH value is adjusted to into 7.0.Mixed liquor is dried in Rotary Evaporators, phenol resin oligomer is obtained.
(2) phenol resin oligomer obtained to step (1) adds dehydrated alcohol, is configured to the phenol that mass fraction is 20%
Urea formaldehyde solution.The butyl titanate of 30ml is added in phenol resin solution, is persistently stirred, is obtained dehydrated alcohol mixed solution (A
That is the first mixed solution).
(3) 2g triblock copolymers are mixed with 20g dehydrated alcohol, is stirred, (B i.e. second mixes to obtain ethanol solution
Close solution).
(4) by 10ml dehydrated alcohol, 4ml distilled water, the mixing of 2ml salpeter solutions;Using carbamide as nitrogen source, add in solution
Plus 15% (urea quality/butyl titanate quality) carbamide;Using ferric nitrate as source of iron, add 11% (ferric nitrate in solution
Quality/butyl titanate quality) ferric nitrate;Obtain mixed solution (C i.e. the 3rd mixed solution).
(5) solution (A) is mixed with solution (B), stirs 25min;Solution (C) is slowly dropped into by mixing by dropper subsequently
Solution, keeps solution in state is stirred vigorously, 40min is persistently stirred after completion of dropwise addition, until forming colloidal sol during Deca.
(6) colloidal sol is aged 12h at room temperature, then gained gel is placed in 100 DEG C of drying baker and is dried 8h, make residual
Ethanol and moisture evaporation in the gel totally, is obtained dried powder.
(7) by dried powder in a nitrogen atmosphere, 850 DEG C of insulations are to slowly warm up to 1 DEG C/min, calcine 4h, that is, obtain
The catalyst of the present invention.
Surface area and pore structure study are carried out to the catalyst of the present invention, using Micromeritics companies of the U.S.
ASAP2020 surface areas and pore structure study instrument, with high pure nitrogen as adsorbate, under liquid nitrogen temperature (77.3K), test sample
BET specific surface area, pore-size distribution feature is measured with BJH adsorption curves.The BET specific surface area of self-control nano titanium dioxide powder
For 42m2/ g, the ferrum nitrogen-doped titanium dioxide of the present invention are averagely reachable with the photocatalyst BET specific surface area that mesoporous carbon is combined
300m2/ more than g, 300-400m2/g;Pore-size distribution is obtained in 3-4.5nm.
That absorbance test is carried out to the catalyst and comparative example of the present invention, using Japanese Shimadzu
SHIMADZUShimadzuUV-3600 type UV, visible light near-infrared spectrophotometers, test ferrum N doping is to titanium dioxide in purple
Outward, the response of visible region.When ferric nitrate/butyl titanate mass ratio is that 5%, carbamide/butyl titanate mass ratio is 5% codope
When, absorption spectrum is substantially moved to visible region, and absorbance increase;When ferric nitrate is brought up to the doping of carbamide
10%, absorbance continues increase.Both of which is apparently higher than pure titinium dioxide powder.
Application of the catalyst of the present invention in nitric oxide photocatalysis, under ultraviolet-visible light, oxygen is participated in vapor
When, it is HNO by NO photocatalytic conversions3And HNO2, photocatalyst surface is attached to, the desorption of product is capable of achieving by washing, immersion
With the regeneration of photocatalyst.
Photocatalyst catalyzed conversion NO experimental systems, mainly by air distribution system, moisture control system, fixed bed reaction system
Constitute Deng three parts.Air distribution system is made up of gas cylinder, air relief valve, mass flowmenter, mixed gas tank and gas piping etc..Simulation
Water vapor concentration (percentage by volume) 35%, oxygen concentration (percentage by volume) 21%, NO concentration 10ppm in gas, remaining is
Nitrogen, simulation gas flow are 1L/min.
Moisture control system is made up of Drexel bottle, bypass, humiture instrument etc..By a certain amount of N2Vapor is carried with bubble type
Into mixed gas tank, with O2、NO、N2Etc. gas mixing, water vapor concentration carries N by adjusting2Flow-control.Simulation gas is entered
Bypass is can switch to before reaction tube, water vapor concentration is measured by German TESTO635-2 types humiture instrument, as shown in Figure 7.Gu
Fixed bed response system is made up of crystal reaction tube, ultraviolet-visible lamp, ferrum cover.Quartz reaction bore 50mm, external diameter 54mm, can
The length for supporting is 100mm.Ultraviolet-visible light lamp (dominant wavelength 365nm, power 250W) is placed above reaction tube at 200mm, outward
The cast iron cover of cover lucifuge.1.0000g photocatalysts are laid in crystal reaction tube during experiment, and are continued into crystal reaction tube
It is passed through simulation gas.
Continue light-catalyzed reaction time respectively 20min, 40min and 60min.After reaction terminates, from crystal reaction tube
Take out photocatalyst, be immersed under room temperature in 20ml deionized waters, soak time is 3h, with fully by product from photocatalyst table
Emaciated face is attached.Jing after filtration is processed, using in ion chromatograph (U.S. wear peace ICS-1100 type ion chromatographs) analysis filtrate from
The concentration of son.Jing is analyzed, and contains certain density NO in filtrate3 -And NO2 -Ion, can be calculated NO in soak3 -And NO2 -
Total ion concentration, and then obtain the amount of the NO of unit mass photocatalyst conversion in certain response time.
In formula:——NO3 -The amount (mol/g) of material
--- measure NO3 -Concentration (mg/L)
In formula:——NO2 -The amount (mol/g) of material
--- measure NO2 -Concentration (mg/L)
In formula:NNO--- unit mass photocatalyst converts the amount (mol/g) of NO materials
Impact of 1 response time of table to NO inversion quantities and product amount
The NO that the photocatalyst of experimental analysiss 5% nitrogen of unit mass -5% Fe2O3 doping was converted within the differential responses time is total
Amount, and NO3 -And NO2 -Change of the ion with the response time.As the response time increases, the inversion quantity of NO increases, while NO3 -
The amount of ion increases, and NO2 -The amount of ion is gradually lowered, and illustrates the NO of photocatalyst surface2 -Ion meeting continued oxidation is NO3 -
Ion.
Impact of 2 mix ratio of table to NO inversion quantities and product amount
During the different nitrogen Fe2O3 doping amounts of experimental analysiss, NO total amounts that photocatalyst is converted in 40min, and product NO3 -
And NO2 -Total ion concentration.As nitrogen-Fe2O3 doping ratio gradually increases, the NO total amounts of conversion first increase to be reduced afterwards, in 5% nitrogen -5%
Maximum is reached during Fe2O3 doping amount.Product NO3 -The amount of ion compares NO2 -The amount of ion is order of magnitude greater, determines that NO is converted
Amount.
The adjustment of technological parameter is carried out according to the record of present invention part, the catalyst of the present invention can be prepared, and
Basically identical property is shown with above-described embodiment.
Exemplary description is done above to the present invention, it should explanation, in the situation of the core without departing from the present invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent of creative work equal
Fall into protection scope of the present invention.
Claims (5)
1. application of the composite catalyst based on ferrum nitrogen-doped titanium dioxide in nitric oxide photocatalysis, it is characterised in that
Under the conditions of ultraviolet visible light, oxygen and vapor participate in reaction, are HNO by NO photocatalytic conversions3And HNO2, mixed based on ferrum nitrogen
300-the 400m of specific surface area of the composite catalyst of miscellaneous titanium dioxide2/ g, pore-size distribution is in 3-4.5nm, composite photo-catalyst
Carbon with anatase titanium dioxide and graphite microcrystal form, and elemental nitrogen and ferrum are to TiO2Lattice is doped.
2. the composite catalyst based on ferrum nitrogen-doped titanium dioxide according to claim 1 is in nitric oxide photocatalysis
Using, it is characterised in that the composite catalyst based on ferrum nitrogen-doped titanium dioxide is carried out as steps described below:
Step 1, by the first mixed solution and the second mixed solution mix homogeneously, then the 3rd mixed solution of Deca thereto, in drop
Plus during be kept stirring for state and persistently stir after completion of dropwise addition, until forming colloidal sol;
Step 2, the vitreosol that step 1 is obtained are aged 8-12 hours under 20-25 degrees Celsius of room temperature, by the gel for obtaining
It is placed in 100-110 DEG C and is dried 8-10h, give full play to the ethanol and moisture that residue in gel, dried powder is obtained;
Step 3, dried powder prepared by step 2 in a nitrogen atmosphere, with the programming rate of 1-2 DEG C/min from room temperature 20-25
Degree Celsius 800-850 DEG C is warming up to, the insulation under 800-850 degrees Celsius carries out calcining 2-4h, obtains composite catalyst;
In step 1, the first mixed solution is prepared as steps described below:
Step 1,20-30 mass parts phenol is melted at 40 DEG C, is added dropwise over 45-55 mass parts mass percents thereto and is
The NaOH aqueous solutions of 20wt%, are then added dropwise over the formalin that 40-45 mass parts mass percents are 37%, will obtain
Mixed liquor 100-150 turns at 70 DEG C/mixing speed of min stirring 1-2h, be cooled to 20-25 degrees Celsius of room temperature, use
Mixed liquor pH value is adjusted to 7.0 by the aqueous solution of the HCl of 0.5mol/L, then mixed liquor is dried in Rotary Evaporators, obtains phenol
Urea formaldehyde oligomer;In Deca, 3-5ml per minute is controlled;
Step 2, adds dehydrated alcohol to phenol resin oligomer prepared by step 1, is configured to the quality of phenol resin oligomer
Phenol resin solution of the percent for 10-20%, adds the butyl titanate of 20-35 parts by volume, stirring in phenol resin solution
Uniformly, obtain the first mixed solution;
In step 1, the second mixed solution is prepared as steps described below:By the Polyethylene oxide-polyoxy third of 1-3 mass parts
Alkene-polyoxyethylene copolymer mixes and is uniformly dispersed with the dehydrated alcohol of 15-25 mass parts, obtains the second mixed solution, described
The number-average molecular weight of polyoxyethylene-poly-oxypropylene polyoxyethylene copolymer is 1000-2200;
In step 1, the 3rd mixed solution is prepared as steps described below:By 10-20 parts by volume dehydrated alcohol, 2-4 volumes
Part distilled water, the mixing of 1-2 parts by volume aqueous solution of nitric acid, in aqueous solution of nitric acid, the mass percent of nitric acid is 10-20%, to
Wherein add carbamide and ferric nitrate respectively as nitrogen source and source of iron, carbamide addition quality and butyl titanate mass ratio for (0.6-
15):100, ferric nitrate addition quality is (0.6-15) with butyl titanate mass ratio:100;Wherein carbamide adds quality and metatitanic acid
Butyl ester mass ratio is (1-5):100, ferric nitrate addition quality is (1-5) with butyl titanate mass ratio:100;In step 1,
The volume of the first mixed solution and the second mixed solution is consistent, is 1-2 times of the 3rd mixed liquor volume.
3. the composite catalyst based on ferrum nitrogen-doped titanium dioxide according to claim 2 is in nitric oxide photocatalysis
Using, it is characterised in that the specific surface area of composite photo-catalyst is 320-350m2/g。
4. the composite catalyst based on ferrum nitrogen-doped titanium dioxide according to claim 2 is in nitric oxide photocatalysis
Using, it is characterised in that in step 3,820-840 degrees Celsius are warming up to, calcine 2.5-3.5 hours.In step 2, it is aged
Time is 10-12 hours.
5. the composite catalyst based on ferrum nitrogen-doped titanium dioxide according to claim 2 is in nitric oxide photocatalysis
Using, it is characterised in that in step 1, during by the first mixed solution and the second mixed solution mix homogeneously, select mechanical agitation
100-200 turns/min, mixing time is 15-25min;State is kept stirring for during Deca and is continued after completion of dropwise addition
20-40min is persistently stirred in stirring, 100-200 turns of mechanical agitation/min after completion of dropwise addition;Deca process adopts at the uniform velocity Deca,
10-30min of Deca used time.
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