CN106560230B - Application of the composite catalyst based on iron nitrogen-doped titanium dioxide in nitric oxide photocatalysis - Google Patents
Application of the composite catalyst based on iron nitrogen-doped titanium dioxide in nitric oxide photocatalysis Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 37
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 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 16
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 46
- 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
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 31
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000005011 phenolic resin Substances 0.000 claims abstract description 27
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004202 carbamide Substances 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000011941 photocatalyst Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 81
- 239000011259 mixed solution Substances 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 27
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 17
- 229910017604 nitric acid Inorganic materials 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229960004756 ethanol Drugs 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 8
- -1 polyoxyethylene copolymer Polymers 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- 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
- 238000010438 heat treatment Methods 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
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 12
- 239000007788 liquid Substances 0.000 abstract description 9
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000356 contaminant Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000003980 solgel method Methods 0.000 abstract description 3
- 238000003795 desorption Methods 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
- 229920000570 polyether Polymers 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 12
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 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
- 230000002045 lasting effect Effects 0.000 description 5
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 5
- 230000035484 reaction time Effects 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
- 239000000523 sample Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 229910011208 Ti—N Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000000862 absorption spectrum 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
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000005516 engineering process Methods 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
- 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
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- 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
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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
- B01J35/60—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
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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
- B01J35/60—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 present invention discloses application of the composite catalyst based on iron nitrogen-doped titanium dioxide in nitric oxide photocatalysis, using be dispersed with the phenol resin oligomer of butyl titanate, liquid polyethers and dehydrated alcohol mixture and containing urea, ferric nitrate solution as raw material, be prepared using a sol-gel process.Nano-titanium dioxide is distributed in mesoporous carbon surface, expands the contact area with target contaminant；The nitrogen co-doped raising light utilization efficiency of iron-and photocatalysis efficiency；By a collosol and gel and roasting process, titanium dioxide is realized in conjunction with mesoporous carbon structure, step is simple, low energy consumption.It is HNO by NO photocatalytic conversion when oxygen and vapor participate under ultraviolet-visible light3And HNO2, it is attached to photocatalyst surface, the regeneration of desorption and photochemical catalyst by washing, impregnating achievable product.
Description
Technical field
The invention belongs to photocatalysis technology fields, more specifically, are related to a kind of iron nitrogen-doped titanium dioxide and mesoporous
Composite photo-catalyst of carbon and preparation method thereof.
Background technique
Anatase titanium dioxide can photocatalytic pollutant degradation, and have the characteristics that low energy consumption, without secondary pollution,
The fields such as air cleaning, wastewater treatment are widely applied.However titanium dioxide forbidden bandwidth with higher, it can only be shorter by wavelength
Ultraviolet excitation, it is low to sun light utilization efficiency (about 3%-5%).Secondly, photohole and electronics be to easily compound, so that dioxy
The photocatalysis efficiency for changing titanium is lower.Third mostly uses Study on Synthesis of Nanocrystal Titanium Dionide powder at present, is using
It needs to support in journey.The contact area of nano-titanium dioxide and target contaminant is equally to influence titanium dioxide optical catalyst benefit
An important factor for rate.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of iron nitrogen-doped titanium dioxide and mesoporous carbons
Composite photo-catalyst and preparation method thereof, by the preparation process of iron nitrogen-doped titanium dioxide and the organic knot of mesoporous carbon forming process
It closes, using a sol-gel process, synchronizes and prepare titanium dioxide and mesoporous carbon materials, this forming process makes titanium dioxide
It is effectively crosslinked with carbon structure, titanium dioxide is evenly distributed in carbon structure, and a collosol and gel and roasting process, is simplified
Preparation step, reduces energy consumption.
Technical purpose of the invention is achieved by following technical proposals:
Iron nitrogen-doped titanium dioxide and the composite photo-catalyst of hollow carbon and preparation method thereof carry out as steps described below:
Step 1, the first mixed solution and the second mixed solution are uniformly mixed, then third mixed solution are added dropwise thereto,
It is kept stirring state during dropwise addition and is persistently stirred after completion of dropwise addition, until forming (transparent) colloidal sol；
Step 2, vitreosol step 1 obtained is aged 8-12 hours under 20-25 degrees Celsius of room temperature, by what is obtained
Gel is placed in 100-110 DEG C dry 8-10h, makes to remain on ethyl alcohol and moisture in gel and gives full play to, and xeraphium is made
End；
Step 3, the dried powder prepared by step 2 in a nitrogen atmosphere, with the heating rate of 1-2 DEG C/min from room temperature
20-25 degrees Celsius are warming up to 800-850 DEG C, and heat preservation carries out calcining 2-4h under 800-850 degrees Celsius, obtain iron N doping two
The composite photo-catalyst of titanium oxide and mesoporous carbon.
In the above-mentioned technical solutions, 300-400m of specific surface area of composite photo-catalyst2/ g, preferably 320-350m2/g。
In the above-mentioned technical solutions, 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 composite photo-catalyst of the invention, the addition of nitrogen source, source of iron changes the combination energy peak position of Ti and O, explanation
Two kinds of ions have effectively entered TiO2Lattice net, and obviously increased after adulterating in visible light region absorption spectrum.
In the above-mentioned technical solutions, in step 3,820-840 degrees Celsius are warming up to, is calcined 2.5-3.5 hours.
In the above-mentioned technical solutions, in step 2, digestion time is 10-12 hours.
In the above-mentioned technical solutions, in step 1, when the first mixed solution and the second mixed solution being uniformly mixed, choosing
100-200 turns of mechanical stirring/min is selected, mixing time is 15-25min.
In the above-mentioned technical solutions, in step 1, it is kept stirring state during dropwise addition and continues after completion of dropwise addition
Stirring, 100-200 turns of mechanical stirring/min persistently stir 20-40min after completion of dropwise addition.
In the above-mentioned technical solutions, in step 1,10-30min of used time is added dropwise using being at the uniform velocity added dropwise in dropwise addition process.
In the above-mentioned technical solutions, 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, 45-55 mass parts quality percentage is added dropwise thereto
Number is the NaOH aqueous solution (sodium hydroxide quality/sodium hydroxide and water quality sum) of 20wt%, and 40-45 is then added dropwise
The formalin (formaldehyde quality/formaldehyde and water quality sum) that mass parts mass percent is 37%, the mixing that will be obtained
Liquid 100-150 turns at 70 DEG C/mixing speed of min stirs 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 7.0, then it is mixed liquor is dry in Rotary Evaporators, it is low to obtain phenolic resin
Polymers；When being added dropwise, 3-5ml per minute is controlled；
Step 2, dehydrated alcohol is added in the phenol resin oligomer prepared to step 1, is configured to phenol resin oligomer
Mass percent is phenol resin solution (phenol resin oligomer quality/phenol resin oligomer and the dehydrated alcohol of 10-20%
Quality sum), into phenol resin solution be added 20-35 parts by volume butyl titanate, stir evenly, it is molten to obtain the first mixing
Liquid.
In the above-mentioned technical solutions, in step 1, the second mixed solution is prepared as steps described below:
By the polyoxyethylene-poly-oxypropylene polyoxyethylene copolymer of 1-3 mass parts, (CAS is numbered as 106392-12-5)
It mixes and is uniformly dispersed with the dehydrated alcohol of 15-25 mass parts, obtain the second mixed solution, due to being mixed with dehydrated alcohol, gather
Ethylene oxide-polyoxypropylene polyoxyethylene copolymer selects liquid form, can carry out molecular weight selection and city according to liquid form
Purchase, the number-average molecular weight of the preferably described polyoxyethylene-poly-oxypropylene polyoxyethylene copolymer are 1000-2200.
In the above-mentioned technical solutions, in step 1, third mixed solution is prepared as steps described below:
10-20 parts by volume dehydrated alcohol, 2-4 parts by volume distilled water, 1-2 parts by volume aqueous solution of nitric acid are mixed, in nitric acid
In aqueous solution, the mass percent of nitric acid is 10-20%, adds urea and ferric nitrate thereto respectively as nitrogen source and source of iron,
Urea adds quality and butyl titanate mass ratio is (0.6-15): 100, ferric nitrate adds quality with butyl titanate mass ratio and is
(0.6-15): 100；Wherein urea 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 the above-mentioned technical solutions, in step 1, the volume of the first mixed solution and the second mixed solution is consistent, is
1-2 times of third mixed liquor volume.
XRD characterization is carried out to catalyst of the invention, the use of instrument is Rigaku D/MAX2500 type X-ray diffractometer
(XRD), light source is CuK- α (λ=0.15418nm monochromator) ray, tube voltage 40kV, tube current 30mA, Scanning step
0.02 °, 3 °/min of sweep speed.Iron nitrogen-doped titanium dioxide and the compound photochemical catalyst of mesoporous carbon are tested, is occurred apparent sharp
Titanium ore phase titanic oxide diffraction maximum illustrates to have obtained the anatase titanium dioxide with photocatalysis performance；There is graphite state
Carbon diffraction maximum, illustrate carbon using class graphite microcrystal as principal mode.
XPS characterization is carried out to catalyst of the invention, the use of instrument is U.S. Perkin Elmer company PHI-1600 type X
X-ray photoelectron spectroscopy X instrument (XPS), Al K α anode, 1486.6eV irradiation sample excites photoelectron, using dome-type precise electronic
Energy analyzer, it is fixed to pass through energy mode.Narrow spectrum scanning is 50eV by energy PE, and full scan is by that can be 187.85eV, with C
1s (284.6eV) is calibration standard.Test iron nitrogen-doped titanium dioxide and the compound photochemical catalyst of mesoporous carbon, detect C, Ti,
O, the presence of N and Fe element.By Fe2p spectral peak, in the characteristic peak of 710.4eV, infer that the Fe element in sample is mainly deposited with+trivalent
?.By N1s spectral peak, 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 peak, after doping iron, nitrogen, the peak O1s combines energy direction 533.3eV characteristic peak occur to height, illustrates in doping iron, nitrogen
Afterwards, increase a kind of oxygen of bonding state, it was demonstrated that the addition of two kinds of elements has an impact the chemical state of oxygen, i.e. removing elemental nitrogen pair
TiO2Lattice is doped except entrance, and elemental iron enters TiO to a certain extent2Lattice.
Compared with prior art, the present invention propose a kind of iron nitrogen-doped titanium dioxide and the compound photochemical catalyst of mesoporous carbon and
Preparation method makes during nano-titanium dioxide is distributed in by nano-titanium dioxide preparation process in conjunction with mesoporous carbon preparation process
Hole carbon surface；And nitrogen, iron ion are adulterated in titanium dioxide forming process, improve visible light-responded range and photocatalysis efficiency.
It using a sol-gel process, synchronizes and prepares titanium dioxide and mesoporous carbon materials, realize that titanium dioxide is effectively handed over carbon structure
Connection, is evenly distributed in titanium dioxide in carbon structure, expands the contact area of photochemical catalyst and pollutant.Mesoporous duct simultaneously
The diffusion for being conducive to contaminant molecule and product molecule, the composite photo-catalyst specific surface area finally prepared are average up to 300m2/
G or more.In titanium dioxide preparation process, nitrogen source and source of iron is added, nitrogen, iron ion is made to effectively enter TiO2Lattice net promotees
Entering light catalyst is responded in visible-range, and improves photocatalysis efficiency.The present invention passes through a collosol and gel and roasting process,
The compound of iron nitrogen-doped titanium dioxide and mesoporous carbon structure is realized simultaneously, is simplified preparation step, is reduced energy consumption.
Detailed description of the invention
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 catalyst of the present invention and the absorbance comparison diagram of comparative catalyst.
Fig. 7 is the structural schematic diagram of photochemical catalyst catalyzed conversion NO experimental system used in the embodiment of the present invention.
Specific embodiment
Technical solution of the present invention is further illustrated combined with specific embodiments below.Commercially available one base Industrial Co., Ltd. of Shanghai
Polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO) F127, uses as triblock copolymer；It is water-soluble to configure nitric acid
Liquid, the mass percent of nitric acid are 20%；Sodium hydrate aqueous solution is configured, the mass percent of sodium hydroxide is 20%；Configuration
Formalin, the mass percent of formaldehyde are 37%.It is stirred in each step using mechanical stirring, mixing speed is stablized
100-120 turns/min.In the technical solution of the present invention, each mass parts are 1g, and each parts by volume is 1mL, and the first mixing is molten
Liquid, the second mixed solution are consistent with dosage (by volume) of third mixed solution.Titanium dioxide powder is prepared using following methods
End is tested as a comparison case:
(1) 8.5mL butyl titanate is mixed with 30mL dehydrated alcohol at room temperature, mechanical stirring 30min obtains clarifying molten
Liquid；
(2) 1.5mL tri-distilled water, 15mL dehydrated alcohol and 1.0mL nitric acid are mixed, obtains solution；
(3) solution prepared by step 2 is slowly dropped into solution prepared by step 1 by dropper, is kept during being added dropwise
Solution is in and is vigorously stirred state, and 30min is persistently stirred after completion of dropwise addition, until formation vitreosol, dropwise addition used time are
20min；
(4) colloidal sol is aged 10h at room temperature, gained gel is then placed in 105 DEG C of drying boxes dry 4h, makes to remain
In in gel ethyl alcohol and moisture evaporation totally, be made dried powder；
(5) powder is warming up to 500 DEG C of heat preservations with 5 DEG C/min, calcines 2h to get control sample titania powder is arrived.
When carrying out the preparation of catalyst of the present invention, the first mixed solution, the second mixed solution and the are prepared respectively first
Three mixed solutions, then carry out solation, ageing, drying and calcination.
Embodiment 1
(1) 25g phenol is melted at 40 DEG C, the NaOH aqueous solution that 50g concentration is 20% is added dropwise, then adds dropwise
Enter the formalin that 42g concentration is 37%.Mixed liquor stirs 1h at 70 DEG C, is cooled to room temperature, with 0.5mol/L HCl solution
Mixed liquor pH value is adjusted to 7.0.Mixed liquor is dry in Rotary Evaporators, obtain phenol resin oligomer.
(2) dehydrated alcohol is added in the phenol resin oligomer obtained to step (1), is configured to the phenol that mass fraction is 15%
Urea formaldehyde solution.The butyl titanate of 25ml is added into phenol resin solution, it is lasting to stir, obtain dehydrated alcohol mixed solution (A
That is the first mixed solution).
(3) 2g triblock copolymer is mixed with 18g dehydrated alcohol, is stirred, obtaining ethanol solution, (B i.e. second is mixed
Close solution).
(4) 15ml dehydrated alcohol, 3ml distilled water, 1ml nitric acid solution are mixed；Using urea as nitrogen source, add into solution
Add the urea of 5% (urea quality/butyl titanate quality)；Using ferric nitrate as source of iron, 5% (nitric acid irony is added into solution
Amount/butyl titanate quality) ferric nitrate；Obtain mixed solution (C i.e. third mixed solution).
(5) solution (A) is mixed with solution (B), stirs 20min；Solution (C) is then slowly dropped by mixing by dropper
Solution keeps solution to be in and is vigorously stirred state, 30min is persistently stirred after completion of dropwise addition during being added dropwise, until forming colloidal sol.
(6) colloidal sol is aged 8h at room temperature, gained gel is then placed in 105 DEG C of drying boxes dry 8h, makes to remain
In in gel ethyl alcohol and moisture evaporation totally, be made dried powder.
(7) in a nitrogen atmosphere by dried powder, 800 DEG C of heat preservations are to slowly warm up to 1 DEG C/min, calcine 2h to get arriving
Catalyst of the invention.
Embodiment 2
(1) 20g phenol is melted at 40 DEG C, the NaOH aqueous solution that 45g concentration is 20% is added dropwise, then adds dropwise
Enter the formalin that 40g concentration is 37%.Mixed liquor stirs 1h at 70 DEG C, is cooled to room temperature, with 0.5mol/L HCl solution
Mixed liquor pH value is adjusted to 7.0.Mixed liquor is dry in Rotary Evaporators, obtain phenol resin oligomer.
(2) dehydrated alcohol is added in the phenol resin oligomer obtained to step (1), is configured to the phenol that mass fraction is 20%
Urea formaldehyde solution.The butyl titanate of 35ml is added into phenol resin solution, it is lasting to stir, obtain dehydrated alcohol mixed solution (A
That is the first mixed solution).
(3) 1g triblock copolymer is mixed with 25g dehydrated alcohol, is stirred, obtaining ethanol solution, (B i.e. second is mixed
Close solution).
(4) 20ml dehydrated alcohol, 2ml distilled water, 2ml nitric acid solution are mixed；Using urea as nitrogen source, add into solution
Add the urea of 10% (urea quality/butyl titanate quality)；Using ferric nitrate as source of iron, 10% (ferric nitrate is added into solution
Quality/butyl titanate quality) ferric nitrate；Obtain mixed solution (C i.e. third mixed solution).
(5) solution (A) is mixed with solution (B), stirs 15min；Solution (C) is then slowly dropped by mixing by dropper
Solution keeps solution to be in and is vigorously stirred state, 20min is persistently stirred after completion of dropwise addition during being added dropwise, until forming colloidal sol.
(6) colloidal sol is aged 12h at room temperature, gained gel is then placed in 100 DEG C of drying boxes dry 10h, is made residual
Stay in gel ethyl alcohol and moisture evaporation totally, be made dried powder.
(7) in a nitrogen atmosphere by dried powder, 850 DEG C of heat preservations are to slowly warm up to 2 DEG C/min, calcine 4h to get arriving
Catalyst of the invention.
Embodiment 3
(1) 30g phenol is melted at 40 DEG C, the NaOH aqueous solution that 50g concentration is 20% is added dropwise, then adds dropwise
Enter the formalin that 40g concentration is 37%.Mixed liquor stirs 1h at 70 DEG C, is cooled to room temperature, with 0.5mol/L HCl solution
Mixed liquor pH value is adjusted to 7.0.Mixed liquor is dry in Rotary Evaporators, obtain phenol resin oligomer.
(2) dehydrated alcohol is added in the phenol resin oligomer obtained to step (1), is configured to the phenol that mass fraction is 20%
Urea formaldehyde solution.The butyl titanate of 25ml is added into phenol resin solution, it is lasting to stir, obtain dehydrated alcohol mixed solution (A
That is the first mixed solution).
(3) 3g triblock copolymer is mixed with 15g dehydrated alcohol, is stirred, obtaining ethanol solution, (B i.e. second is mixed
Close solution).
(4) 20ml dehydrated alcohol, 4ml distilled water, 1ml nitric acid solution are mixed；Using urea as nitrogen source, add into solution
Add the urea of 8% (urea quality/butyl titanate quality)；Using ferric nitrate as source of iron, 10% (nitric acid irony is added into solution
Amount/butyl titanate quality) ferric nitrate；Obtain mixed solution (C i.e. third mixed solution).
(5) solution (A) is mixed with solution (B), stirs 20min；Solution (C) is then slowly dropped by mixing by dropper
Solution keeps solution to be in and is vigorously stirred state, 20min is persistently stirred after completion of dropwise addition during being added dropwise, until forming colloidal sol.
(6) colloidal sol is aged 10h at room temperature, gained gel is then placed in 110 DEG C of drying boxes dry 9h, makes to remain
In in gel ethyl alcohol and moisture evaporation totally, be made dried powder.
(7) in a nitrogen atmosphere by dried powder, 820 DEG C of heat preservations are to slowly warm up to 1 DEG C/min, calcine 3h to get arriving
Catalyst of the invention.
Embodiment 4
(1) 30g phenol is melted at 40 DEG C, the NaOH aqueous solution that 55g concentration is 20% is added dropwise, then adds dropwise
Enter the formalin that 40g concentration is 37%.Mixed liquor stirs 1h at 70 DEG C, is cooled to room temperature, with 0.5mol/L HCl solution
Mixed liquor pH value is adjusted to 7.0.Mixed liquor is dry in Rotary Evaporators, obtain phenol resin oligomer.
(2) dehydrated alcohol is added in the phenol resin oligomer obtained to step (1), is configured to the phenol that mass fraction is 20%
Urea formaldehyde solution.The butyl titanate of 35ml is added into phenol resin solution, it is lasting to stir, obtain dehydrated alcohol mixed solution (A
That is the first mixed solution).
(3) 1g triblock copolymer is mixed with 15g dehydrated alcohol, is stirred, obtaining ethanol solution, (B i.e. second is mixed
Close solution).
(4) 20ml dehydrated alcohol, 3ml distilled water, 2ml nitric acid solution are mixed；Using urea as nitrogen source, add into solution
Add the urea of 0.6% (urea quality/butyl titanate quality)；Using ferric nitrate as source of iron, 0.4% (nitric acid is added into solution
Weight of iron/butyl titanate quality) ferric nitrate；Obtain mixed solution (C i.e. third mixed solution).
(5) solution (A) is mixed with solution (B), stirs 15min；Solution (C) is then slowly dropped by mixing by dropper
Solution keeps solution to be in and is vigorously stirred state, 30min is persistently stirred after completion of dropwise addition during being added dropwise, until forming colloidal sol.
(6) colloidal sol is aged 12h at room temperature, gained gel is then placed in 110 DEG C of drying boxes dry 8h, makes to remain
In in gel ethyl alcohol and moisture evaporation totally, be made dried powder.
(7) in a nitrogen atmosphere by dried powder, 830 DEG C of heat preservations are to slowly warm up to 2 DEG C/min, calcine 2h to get arriving
Catalyst of the invention.
Embodiment 5
(1) 30g phenol is melted at 40 DEG C, the NaOH aqueous solution that 45g concentration is 20% is added dropwise, then adds dropwise
Enter the formalin that 40g concentration is 37%.Mixed liquor stirs 1h at 70 DEG C, is cooled to room temperature, with 0.5mol/L HCl solution
Mixed liquor pH value is adjusted to 7.0.Mixed liquor is dry in Rotary Evaporators, obtain phenol resin oligomer.
(2) dehydrated alcohol is added in the phenol resin oligomer obtained to step (1), is configured to the phenol that mass fraction is 20%
Urea formaldehyde solution.The butyl titanate of 30ml is added into phenol resin solution, it is lasting to stir, obtain dehydrated alcohol mixed solution (A
That is the first mixed solution).
(3) 2g triblock copolymer is mixed with 20g dehydrated alcohol, is stirred, obtaining ethanol solution, (B i.e. second is mixed
Close solution).
(4) 10ml dehydrated alcohol, 4ml distilled water, 2ml nitric acid solution are mixed；Using urea as nitrogen source, add into solution
Add the urea of 15% (urea quality/butyl titanate quality)；Using ferric nitrate as source of iron, 11% (ferric nitrate is added into solution
Quality/butyl titanate quality) ferric nitrate；Obtain mixed solution (C i.e. third mixed solution).
(5) solution (A) is mixed with solution (B), stirs 25min；Solution (C) is then slowly dropped by mixing by dropper
Solution keeps solution to be in and is vigorously stirred state, 40min is persistently stirred after completion of dropwise addition during being added dropwise, until forming colloidal sol.
(6) colloidal sol is aged 12h at room temperature, gained gel is then placed in 100 DEG C of drying boxes dry 8h, makes to remain
In in gel ethyl alcohol and moisture evaporation totally, be made dried powder.
(7) in a nitrogen atmosphere by dried powder, 850 DEG C of heat preservations are to slowly warm up to 1 DEG C/min, calcine 4h to get arriving
Catalyst of the invention.
Surface area and pore structure study are carried out to catalyst of the invention, use Micromeritics company, the U.S.
ASAP2020 surface area and pore structure study instrument, using high pure nitrogen as adsorbate, at liquid nitrogen temperature (77.3K), test sample
BET specific surface area, pore-size distribution feature is measured with BJH adsorption curve.Make the BET specific surface area of nano titanium dioxide powder by oneself
For 42m2/ g, iron nitrogen-doped titanium dioxide of the invention are average reachable with the compound photochemical catalyst BET specific surface area of mesoporous carbon
300m2/ g or more, 300-400m2/g；Pore-size distribution is obtained in 3-4.5nm.
That absorbance test is carried out to catalyst and comparative example of the invention, uses Japanese Shimadzu SHIMADZU
ShimadzuUV-3600 type UV, visible light near-infrared spectrophotometer tests iron N doping to titanium dioxide in ultraviolet, visible light
The response in area.When ferric nitrate/butyl titanate mass ratio is 5%, urea/butyl titanate mass ratio is 5% codope, light is absorbed
Spectrum is obviously mobile to visible light region, and absorbance increases；When the doping of ferric nitrate and urea is increased to 10%, absorbance
Continue to 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 and vapor are participated in
When, it is HNO by NO photocatalytic conversion3And HNO2, it is attached to photocatalyst surface, by the desorption for washing, impregnating achievable product
With the regeneration of photochemical catalyst.
Photochemical catalyst catalyzed conversion NO experimental system, mainly by air distribution system, humidity control system, fixed bed reaction system
Etc. three parts composition.Air distribution system is made of high pressure gas cylinder, pressure reducing 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.
Humidity control system is made 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 mixings, water vapor concentration by adjust carry N2Flow control.Gas is simulated to enter
It can switch to bypass before reaction tube, water vapor concentration measured by German TESTO635-2 type humiture instrument, as shown in Fig. 7.Gu
Fixed bed reaction system is made of crystal reaction tube, ultraviolet-visible lamp, iron cover.Quartz reaction bore 50mm, outer diameter 54mm, can
The length supported is 100mm.Ultraviolet-visible light lamp (dominant wavelength 365nm, power 250W) is placed at 200mm above reaction tube, outside
Cover the cast iron cover being protected from light.1.0000g photochemical catalyst is laid in crystal reaction tube when experiment, and is continued into crystal reaction tube
It is passed through simulation gas.
Continuing the photocatalysis reaction time is respectively 20min, 40min and 60min.After reaction, from crystal reaction tube
Photochemical catalyst is taken out, is immersed in 20ml deionized water at room temperature, soaking time 3h, sufficiently by product from photochemical catalyst table
Emaciated face is attached.After filtration treatment, using in ion chromatograph (U.S. wear peace ICS-1100 type ion chromatograph) analysis filtrate from
The concentration of son.Through analyzing, certain density NO is contained in filtrate3 -And NO2 -Ion can be calculated NO in soak3 -And NO2 -
Total ion concentration, and then obtain the amount for the NO that unit mass photochemical catalyst converts in certain reaction time.
In formula:——NO3 -The amount (mol/g) of substance
--- measure NO3 -Concentration (mg/L)
In formula:——NO2 -The amount (mol/g) of substance
--- measure NO2 -Concentration (mg/L)
In formula: NNO--- the amount (mol/g) of unit mass photochemical catalyst conversion NO substance
Influence of 1 reaction time of table to NO inversion quantity and product amount
The NO that the photochemical catalyst of experimental analysis 5% nitrogen of unit mass -5% Fe2O3 doping converts within the differential responses time is total
Amount and NO3 -And NO2 -Ion with the reaction time variation.As the reaction time increases, the inversion quantity of NO increases, while NO3 -
The amount of ion increases, and NO2 -The amount of ion gradually decreases, and illustrates the NO of photocatalyst surface2 -Ion meeting continued oxidation is NO3 -
Ion.
Influence of 2 mix ratio of table to NO inversion quantity and product amount
When the different nitrogen Fe2O3 doping amounts of experimental analysis, NO total amount and product NO that photochemical catalyst converts in 40min3 -
And NO2 -Total ion concentration.As nitrogen-Fe2O3 doping ratio gradually increases, the NO total amount of conversion first increases to be reduced afterwards, in 5% nitrogen -5%
Reach maximum value when Fe2O3 doping amount.Product NO3 -The amount ratio NO of ion2 -The amount of ion is order of magnitude greater, determines that NO is converted
Amount.
The record of content part carries out the adjustment of technological parameter according to the present invention, can prepare catalyst of the invention, and
Almost the same property is shown with above-described embodiment.
Illustrative description has been done to the present invention above, it should explanation, the case where not departing from core of the invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal
Fall into protection scope of the present invention.
Claims (4)
1. application of the composite catalyst based on iron nitrogen-doped titanium dioxide in nitric oxide photocatalysis, which is characterized in that
Under the conditions of ultraviolet visible light, oxygen and vapor participate in reaction, are HNO by NO photocatalytic conversion3And HNO2, mixed based on iron nitrogen
300-400m 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 iron are to TiO2Lattice is doped；The base
It is carried out as steps described below in the composite catalyst of iron nitrogen-doped titanium dioxide:
Step 1, the first mixed solution and the second mixed solution are uniformly mixed, then third mixed solution is added dropwise thereto, dripped
It is kept stirring state during adding and is persistently stirred after completion of dropwise addition, until forming colloidal sol；
Step 2, vitreosol step 1 obtained is aged 8-12 hours under 20-25 degrees Celsius of room temperature, the gel that will be obtained
It is placed in 100-110 DEG C dry 8-10h, makes to remain on ethyl alcohol and moisture in gel and gives full play to, dried powder is made；
Step 3, the dried powder prepared by step 2 in a nitrogen atmosphere, with the heating rate of 1-2 DEG C/min from room temperature 20-25
Degree Celsius it is warming up to 800-850 DEG C, heat preservation carries out calcining 2-4h under 800-850 degrees Celsius, 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, 45-55 mass parts mass percent is added dropwise thereto is
Then the NaOH aqueous solution of 20wt% is added dropwise the formalin that 40-45 mass parts mass percent is 37%, will obtain
Mixed liquor 100-150 turns at 70 DEG C/mixing speed of min stirs 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 dry in Rotary Evaporators, obtains phenol
Urea formaldehyde oligomer；When being added dropwise, 3-5ml per minute is controlled；
Step 2, dehydrated alcohol is added in the phenol resin oligomer prepared to step 1, is configured to the quality of phenol resin oligomer
Percentage is the phenol resin solution of 10-20%, and the butyl titanate of 20-35 parts by volume, stirring are added into phenol resin solution
Uniformly, the first mixed solution is obtained；
In step 1, the second mixed solution is prepared as steps described below: by polyoxyethylene-polyoxy third of 1-3 mass parts
Alkene-polyoxyethylene copolymer is mixed 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, third mixed solution is prepared as steps described below: by 10-20 parts by volume dehydrated alcohol, 2-4 volume
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
Urea and ferric nitrate are wherein added respectively as nitrogen source and source of iron, urea adds quality and butyl titanate mass ratio is (0.6-
15): 100, ferric nitrate adds quality and butyl titanate mass ratio is (0.6-15): 100；Wherein urea addition quality and metatitanic acid
Butyl ester mass ratio is (1-5): 100, ferric nitrate adds quality and butyl titanate mass ratio is (1-5): 100；In step 1,
The volume of first mixed solution and the second mixed solution is consistent, is 1-2 times of third mixed liquor volume；Each mass parts
For 1g, each parts by volume is 1mL.
2. the composite catalyst according to claim 1 based on iron nitrogen-doped titanium dioxide is in nitric oxide photocatalysis
Using, which is characterized in that the specific surface area of composite photo-catalyst is 320-350m2/g。
3. the composite catalyst according to claim 1 based on iron nitrogen-doped titanium dioxide is in nitric oxide photocatalysis
Using, which is characterized in that in step 3,820-840 degrees Celsius are warming up to, calcined 2.5-3.5 hours；In step 2, it is aged
Time is 10-12 hours.
4. the composite catalyst according to claim 1 based on iron nitrogen-doped titanium dioxide is in nitric oxide photocatalysis
Using, which is characterized in that in step 1, when the first mixed solution and the second mixed solution are uniformly mixed, select mechanical stirring
100-200 turns/min, mixing time is 15-25min；It is kept stirring state during dropwise addition and continues after completion of dropwise addition
Stirring, 100-200 turns of mechanical stirring/min persistently stir 20-40min after completion of dropwise addition；Dropwise addition process is used and is at the uniform velocity added dropwise,
10-30min of used time is added dropwise.
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| CN104107706A (en) * | 2014-07-15 | 2014-10-22 | 西安交通大学 | Preparation method of nitrogen-iron codoped nanometer titania photocatalyst |
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