CN107486228A - A kind of mesopore surfaces defect Fe-N-TiO2Microballoon catalysis material and preparation method thereof - Google Patents
A kind of mesopore surfaces defect Fe-N-TiO2Microballoon catalysis material and preparation method thereof Download PDFInfo
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- CN107486228A CN107486228A CN201610420673.1A CN201610420673A CN107486228A CN 107486228 A CN107486228 A CN 107486228A CN 201610420673 A CN201610420673 A CN 201610420673A CN 107486228 A CN107486228 A CN 107486228A
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- 239000000463 material Substances 0.000 title claims abstract description 42
- 230000007547 defect Effects 0.000 title claims abstract description 26
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 36
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 127
- 235000019441 ethanol Nutrition 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000010936 titanium Substances 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 229910052719 titanium Inorganic materials 0.000 claims description 22
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 238000004062 sedimentation Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 12
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical group CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000007146 photocatalysis Methods 0.000 claims description 5
- 230000001699 photocatalysis Effects 0.000 claims description 5
- 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 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000005121 nitriding Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 2
- 238000005915 ammonolysis reaction Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- RZYKUPXRYIOEME-UHFFFAOYSA-N CCCCCCCCCCCC[S] Chemical compound CCCCCCCCCCCC[S] RZYKUPXRYIOEME-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 238000011017 operating method Methods 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000004005 microsphere Substances 0.000 description 11
- 239000012535 impurity Substances 0.000 description 9
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 9
- 238000003760 magnetic stirring Methods 0.000 description 9
- 239000003643 water by type Substances 0.000 description 9
- 239000011343 solid material Substances 0.000 description 8
- 238000009837 dry grinding Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of mesopore surfaces defect Fe N TiO2Microballoon catalysis material and preparation method thereof.Specifically include the Fe TiO for preparing mesopore surfaces defect2Microballoon and nitridation process step, nitrogen source used in the nitrogen treatment are ammonia, the Fe TiO of the mesopore surfaces defect2Microballoon adds surfactant in preparing.Nitrogen treatment is carried out in ammonia, obtains mesopore surfaces defect Fe N TiO2Microballoon catalysis material, the mesopore surfaces defect Fe N TiO that above-mentioned experimentation obtains2Microballoon catalysis material has meso-hole structure and spherical structure is more homogeneous.
Description
Technical field
The present invention relates to field of material synthesis technology, more particularly to a kind of mesopore surfaces defect Fe-N-TiO2Microballoon light is urged
Change material and preparation method thereof.
Background technology
In recent years, nano-TiO is utilized2The extensive concern for having caused domestic and foreign scholars is purified to organic pollution.But
Relatively low photo-quantum efficiency and slower reaction rate limit TiO2The practicalization of photocatalysis technology.How further to carry
High TiO2Photocatalytic activity turn into current active research topic.To nano-TiO2It is most of that material, which is modified processing,
The method that researcher uses.Conventional method of modifying concentrates on metal-doped, nonmetal doping, noble-metal-supported and semiconductor material
Expect compound etc..
We use transition-metal Fe3+Titania-doped method is modified to material.On this basis to Fe-
TiO2Material carries out nitrogen treatment, obtains the mesopore surfaces defect Fe-N-TiO of bigger serface2Material.The method of nitrogen treatment
Nitrogenized for ammonia atmosphere, while ammonia atmosphere provides N sources, it may have reduction.In Fe-TiO2It is middle to mix the same of N element
When also result in substantial amounts of surface defect.Therefore such material has larger facilitation to photocatalysis.
The content of the invention
It is an object of the invention to provide a kind of mesopore surfaces defect Fe-N-TiO2Microballoon catalysis material and its preparation side
Method.Mesopore surfaces defect Fe-N-TiO of the present invention2Microballoon catalysis material size between 500-600nm, duct is more homogeneous,
Material scatter is good, specific surface area is larger, has good application prospect.
Compared with other method, the present invention has that course of reaction is simple, and the reaction time is short, without any complicated operation and
The advantages that special equipment.
The technical scheme that the present invention takes is：
A kind of mesopore surfaces defect Fe-N-TiO2Microballoon catalysis material, including prepare the Fe-TiO of mesopore surfaces defect2
Microballoon and nitridation process step, nitrogen source used in the nitrogen treatment are ammonia.
The Fe-TiO of the mesopore surfaces defect2Microballoon adds surfactant in preparing.
The present invention also provides a kind of mesopore surfaces defect Fe-N-TiO2The preparation method of microballoon catalysis material, the side
Method includes：Surfactant is dissolved in ethanol solution, after stirring a period of time surfactant fully dissolves, adds iron content
The ethanol solution of compound, water is added, turns down magnetic agitation revolution, finally rapidly joins titanium-containing compound, standing sedimentation after stirring,
Ethanol and/or water washing more than 3 times, drying and grinding obtains powder, and powder is carried out into hydro-thermal reaction afterwards, by the product of gained in sky
A period of time is calcined in gas atmosphere, then carries out high-temperature ammonolysis processing, mesopore surfaces defect Fe-N-TiO is prepared2Microballoon light is urged
Change material.
Surfactant and titanium-containing compound mol ratio are (0.1-2):1；Surfactant preferably rubs with titanium-containing compound
Your ratio is (0.2-2):1, most preferably 0.5：1；The iron containing compoundses include：One kind in ferric nitrate, iron chloride or ferric sulfate
It is or two or more；The titanium-containing compound is more than one or both of isopropyl titanate, titanium tetrachloride or titanyl sulfate；It is described
Surfactant is more than one or both of cetylamine, the octadecylamine or dodecyl sodium sulfate operation before standing
In step, water is added in reaction system, the mol ratio of water and titanium-containing compound is 10-60：1, preferably 10-30:1, most preferably
20:1。
Mesopore surfaces defect Fe-N-TiO2In microballoon catalysis material, Fe and Ti mol ratio are 0.1-10:100；Fe and
Preferred mole of Ti is 0.1-2：100；Ethanol content is 98-99.5wt% in described ethanol solution, during described standing sedimentation
Between be 10-20 hours.
The method of the hydro-thermal reaction is：Powder is transferred to the stainless steel high temperature reaction under high pressure that polytetrafluoroethylene (PTFE) is liner
In kettle, the mixture of second alcohol and water is added as solvent, at 120-180 DEG C, after heating 12-24h, is cooled to room temperature, gained
Product is respectively washed more than 3 times with deionized water and absolute ethyl alcohol, centrifugal filtration, is dried in vacuo at 50-60 DEG C, is obtained Fe-
TiO2Microballoon persursor material.
The volume ratio of second alcohol and water in solvent is (1-3)：1.
Calcining heat is controlled at 400-600 DEG C, calcining heat is preferably 450-550 DEG C；Calcination time control is existed
30min-2h。
The nitrogen source of the nitrogen treatment is ammonia.
Nitriding temperature is 400-600 DEG C；Nitridation time is 30min-2h.
The mesopore surfaces defect Fe-N-TiO that above-mentioned experimentation obtains2Microballoon catalysis material has meso-hole structure and ball
Shape structure is more homogeneous, realizes the purpose of invention.
Obtain mesopore surfaces defect Fe-N-TiO2The synthesis key point of microballoon catalysis material：
1) react isopropyl titanate addition speed in raw material mixing speed reduction, will avoid too fast mixing speed from breaking soon
Bad material morphology；
2) hydrothermal temperature, time control avoid scantling excessive in zone of reasonableness；
3) calcination time is unsuitable too high, on the one hand can destroy product morphology, on the other hand easily cause material crystal transfer.
4) nitriding temperature and time are strictly controlled, appropriate mix N amounts and surface defect have facilitation to photocatalysis.
Brief description of the drawings
Fig. 1 is the mesoporous Fe-TiO prepared2Micro-sphere material and mesopore surfaces defect Fe-N-TiO2Microballoon catalysis material (Fe
Mol ratio with Ti is 1：100) XRD piece.
Fig. 2 is the mesoporous Fe-TiO prepared2Micro-sphere material and mesopore surfaces defect Fe-N-TiO2Microballoon catalysis material (Fe
Mol ratio with Ti is 1：100) SEM pictures.
Fig. 3 is the mesoporous Fe-TiO prepared2Micro-sphere material and mesopore surfaces defect Fe-N-TiO2Microballoon catalysis material (Fe
Mol ratio with Ti is 1：100) UV-vis DRS spectrum picture.
Embodiment
Further illustrated with reference to specific embodiment and comparative example.
Solution is prepared in embodiment 1-3：1.525g ferric nitrates are dissolved in 50mL ethanol solutions (98wt.%), are made into nitre
Sour ferrous solution.
Embodiment 1：
At room temperature, 1.98g cetylamines are completely dissolved in 200mL ethanol solutions (98wt.%), magnetic agitation, added
Iron nitrate solution, while 1.6mL deionized waters are added, magnetic stirring apparatus revolution is finally turned down, is 1/ by Fe and Ti mol ratio
100 rapidly join isopropyl titanate.After stirring 30s, solution left standstill sedimentation 18h.Gains are washed 3 with ethanol and deionized water
Time, drying and grinding.In the stainless steel high temperature autoclave with polytetrafluoroethyllining lining that powder is shifted to a 100mL,
40mL ethanol and 20mL water are added, the hydro-thermal reaction 18h at 160 DEG C is placed in Muffle furnace, is subsequently cooled to room temperature, products therefrom
It is respectively washed three times with water and absolute ethyl alcohol, removes possible remaining impurity, centrifugal filtration, be dried in vacuo at 60 DEG C.Will be dry
Product after dry calcines 2h in air atmosphere at 500 DEG C.Obtain mesoporous Fe-TiO2Micro-sphere material.500 in ammonia atmosphere
DEG C calcining 2h.Obtain mesopore surfaces defect Fe-N-TiO2Microballoon catalysis material (parameter is as shown in Figure 1, Figure 2 and Figure 3).Product
Crystallinity is preferable, pattern uniformly and good dispersion.In addition ammonia atmosphere has reproducibility, and exhibiting high surface occur in material surface lacks
Fall into, have promotion to light-catalyzed reaction.
Embodiment 2：
At room temperature, 1.98g cetylamines are completely dissolved in 200mL ethanol solutions (98wt.%), magnetic agitation, added
Iron nitrate solution, while 1.6mL deionized waters are added, magnetic stirring apparatus revolution is finally turned down, the mol ratio by Fe and Ti is
0.1/100 rapidly joins isopropyl titanate.After stirring 30s, solution left standstill sedimentation 12h.Gains ethanol and deionization are washed
3 times are washed, drying and grinding.Powder is shifted to the 100mL stainless steel high temperature autoclave with polytetrafluoroethyllining lining
In, 40mL ethanol and 20mL water are added, the hydro-thermal reaction 14h at 180 DEG C is placed in Muffle furnace, is subsequently cooled to room temperature, gained
Product is respectively washed three times with water and absolute ethyl alcohol, is removed possible remaining impurity, centrifugal filtration, is dried in vacuo at 60 DEG C.
Dried product at 400 DEG C is calcined into 1h in air atmosphere.400 DEG C of calcining 30min in ammonia atmosphere.Obtain mesoporous
Fe-N-TiO2Microsphere solid material.
Embodiment 3：
At room temperature, 1.98g cetylamines are completely dissolved in 200mL ethanol solutions (98wt.%), magnetic agitation, added
Iron nitrate solution, while 1.6mL deionized waters are added, magnetic stirring apparatus revolution is finally turned down, by Fe and Ti mol ratio 0.2/
100 rapidly join isopropyl titanate.After stirring 30s, solution left standstill sedimentation 12h.Gains are washed 3 with ethanol and deionized water
Time, drying and grinding.In the stainless steel high temperature autoclave with polytetrafluoroethyllining lining that powder is shifted to a 100mL,
45mL ethanol and 15mL water are added, the hydro-thermal reaction 14h at 180 DEG C is placed in Muffle furnace, is subsequently cooled to room temperature, products therefrom
It is respectively washed three times with water and absolute ethyl alcohol, removes possible remaining impurity, centrifugal filtration, be dried in vacuo at 60 DEG C.Will be dry
Product after dry calcines 30min in air atmosphere at 400 DEG C.400 DEG C of calcining 2h in ammonia atmosphere.Obtain mesoporous Fe-
N-TiO2Microsphere solid material.
Embodiment 4：
At room temperature, 1.98g cetylamines are completely dissolved in 200mL ethanol solutions (98wt.%), magnetic agitation, added
Iron nitrate solution, while 1.6mL deionized waters are added, magnetic stirring apparatus revolution is finally turned down, by Fe and Ti mol ratio 0.5/
100 rapidly join isopropyl titanate.After stirring 30s, solution left standstill sedimentation 14h.Gains are washed 3 with ethanol and deionized water
Time, drying and grinding.In the stainless steel high temperature autoclave with polytetrafluoroethyllining lining that powder is shifted to a 100mL,
45mL ethanol and 15mL water are added, the hydro-thermal reaction 14h at 180 DEG C is placed in Muffle furnace, is subsequently cooled to room temperature, products therefrom
It is respectively washed three times with water and absolute ethyl alcohol, removes possible remaining impurity, centrifugal filtration, be dried in vacuo at 60 DEG C.Will be dry
Product after dry calcines 2h in air atmosphere at 400 DEG C.Calcined 30 minutes for 500 DEG C in ammonia atmosphere.Obtain mesoporous Fe-
N-TiO2Microsphere solid material.
Embodiment 5：
At room temperature, 1.98g cetylamines are completely dissolved in 200mL ethanol solutions (98wt.%), magnetic agitation, added
Iron nitrate solution, while 1.6mL deionized waters are added, magnetic stirring apparatus revolution is finally turned down, by Fe and Ti mol ratio 0.8/
100 rapidly join isopropyl titanate.After stirring 30s, solution left standstill sedimentation 14h.Gains are washed 3 with ethanol and deionized water
Time, drying and grinding.In the stainless steel high temperature autoclave with polytetrafluoroethyllining lining that powder is shifted to a 100mL,
30mL ethanol and 30mL water are added, the hydro-thermal reaction 14h at 180 DEG C is placed in Muffle furnace, is subsequently cooled to room temperature, products therefrom
It is respectively washed three times with water and absolute ethyl alcohol, removes possible remaining impurity, centrifugal filtration, be dried in vacuo at 60 DEG C.Will be dry
Product after dry calcines 1h in air atmosphere at 500 DEG C.400 DEG C of calcining 1h in ammonia atmosphere.Obtain mesoporous Fe-N-
TiO2Microsphere solid material.
Embodiment 6：
At room temperature, 1.98g cetylamines are completely dissolved in 200mL ethanol solutions (98wt.%), magnetic agitation, added
Iron nitrate solution, while 1.6mL deionized waters are added, magnetic stirring apparatus revolution is finally turned down, by Fe and Ti mol ratio 2/100
Rapidly join isopropyl titanate.After stirring 30s, solution left standstill sedimentation 16h.Gains are washed 3 times with ethanol and deionized water, done
Dry grinding.In the stainless steel high temperature autoclave with polytetrafluoroethyllining lining that powder is shifted to a 100mL, add
30mL ethanol and 30mL water, the hydro-thermal reaction 24h at 120 DEG C is placed in Muffle furnace, is subsequently cooled to room temperature, products therefrom water
It is respectively washed three times with absolute ethyl alcohol, removes possible remaining impurity, centrifugal filtration, be dried in vacuo at 60 DEG C.After drying
Product calcine 30min at 600 DEG C in air atmosphere.600 DEG C of calcining 2h in ammonia atmosphere.Obtain mesoporous Fe-N-
TiO2Microsphere solid material.
Embodiment 7：
At room temperature, 1.98g cetylamines are completely dissolved in 200mL ethanol solutions (98wt.%), magnetic agitation, added
Iron nitrate solution, while 1.6mL deionized waters are added, magnetic stirring apparatus revolution is finally turned down, by Fe and Ti mol ratio 3/100
Rapidly join isopropyl titanate.After stirring 30s, solution left standstill sedimentation 16h.Gains are washed 3 times with ethanol and deionized water, done
Dry grinding.In the stainless steel high temperature autoclave with polytetrafluoroethyllining lining that powder is shifted to a 100mL, add
40mL ethanol and 20mL water, the hydro-thermal reaction 24h at 120 DEG C is placed in Muffle furnace, is subsequently cooled to room temperature, products therefrom water
It is respectively washed three times with absolute ethyl alcohol, removes possible remaining impurity, centrifugal filtration, be dried in vacuo at 60 DEG C.After drying
Product calcine 1h at 600 DEG C in air atmosphere.600 DEG C of calcining 1h in ammonia atmosphere.Obtain mesoporous Fe-N-TiO2It is micro-
Ball solid material.
Embodiment 8：
At room temperature, 1.98g cetylamines are completely dissolved in 200mL ethanol solutions (98wt.%), magnetic agitation, added
Iron nitrate solution, while 1.6mL deionized waters are added, magnetic stirring apparatus revolution is finally turned down, by Fe and Ti mol ratio 4/100
Rapidly join isopropyl titanate.After stirring 30s, solution left standstill sedimentation 18h.Gains are washed 3 times with ethanol and deionized water, done
Dry grinding.In the stainless steel high temperature autoclave with polytetrafluoroethyllining lining that powder is shifted to a 100mL, add
45mL ethanol and 15mL water, the hydro-thermal reaction 24h at 120 DEG C is placed in Muffle furnace, is subsequently cooled to room temperature, products therefrom water
It is respectively washed three times with absolute ethyl alcohol, removes possible remaining impurity, centrifugal filtration, be dried in vacuo at 60 DEG C.After drying
Product calcine 30min at 500 DEG C in air atmosphere.500 DEG C of calcining 1h in ammonia atmosphere.Obtain mesoporous Fe-N-
TiO2Microsphere solid material.
Embodiment 9：
At room temperature, 1.98g cetylamines are completely dissolved in 200mL ethanol solutions (98wt.%), magnetic agitation, added
Iron nitrate solution, while 1.6mL deionized waters are added, magnetic stirring apparatus revolution is finally turned down, by Fe and Ti mol ratio 10/
100 rapidly join isopropyl titanate.After stirring 30s, solution left standstill sedimentation 20h.Gains are washed 3 with ethanol and deionized water
Time, drying and grinding.In the stainless steel high temperature autoclave with polytetrafluoroethyllining lining that powder is shifted to a 100mL,
30mL ethanol and 30mL water are added, the hydro-thermal reaction 24h at 120 DEG C is placed in Muffle furnace, is subsequently cooled to room temperature, products therefrom
It is respectively washed three times with water and absolute ethyl alcohol, removes possible remaining impurity, centrifugal filtration, be dried in vacuo at 60 DEG C.Will be dry
Product after dry calcines 2h in air atmosphere at 600 DEG C.600 DEG C of calcining 30min in ammonia atmosphere.Obtain mesoporous Fe-
N-TiO2Microsphere solid material.
Claims (10)
- A kind of 1. mesopore surfaces defect Fe-N-TiO2Microballoon catalysis material, it is characterised in that：Including preparing mesopore surfaces defect Fe-TiO2Microballoon and nitridation process step, nitrogen source used in the nitrogen treatment are ammonia.
- 2. catalysis material according to claim 1, it is characterised in that：The Fe-TiO of the mesopore surfaces defect2Microballoon system Standby middle addition surfactant.
- A kind of 3. mesopore surfaces defect Fe-N-TiO2The preparation method of microballoon catalysis material, it is characterised in that：Methods described bag Include：Surfactant is dissolved in ethanol solution, after stirring a period of time surfactant fully dissolves, adds iron containing compoundses Ethanol solution, add water, turn down magnetic agitation revolution, finally rapidly join titanium-containing compound, standing sedimentation after stirring, ethanol And/or water washing more than 3 times, drying and grinding obtains powder, and powder is carried out into hydro-thermal reaction afterwards, by the product of gained in air gas A period of time is calcined in atmosphere, then carries out high-temperature ammonolysis processing, mesopore surfaces defect Fe-N-TiO is prepared2Microballoon photocatalysis material Material.
- 4. preparation method according to claim 3, it is characterised in that：Surfactant is with titanium-containing compound mol ratio (0.1-2):1；Surfactant and titanium-containing compound preferred molar ratio are (0.2-2):1, most preferably 0.5：1；The iron content Compound includes：Ferric nitrate, more than one or both of iron chloride or ferric sulfate；The titanium-containing compound is isopropyl titanate, four It is more than one or both of titanium chloride or titanyl sulfate；The surfactant is cetylamine, octadecylamine or dodecyl sulphur More than one or both of sour sodium, in the operating procedure before standing, water, water and titanium-containing compound are added in reaction system Mol ratio be 10-60：1, preferably 10-30:1, most preferably 20:1.
- 5. preparation method according to claim 3, it is characterised in that：Mesopore surfaces defect Fe-N-TiO2Microballoon photocatalysis material In material, Fe and Ti mol ratio are 0.1-10:100；Preferred mole of Fe and Ti is 0.1-2：100；Second in described ethanol solution Alcohol content is 98-99.5wt%, and the described standing sedimentation time is 10-20 hours.
- 6. preparation method according to claim 3, it is characterised in that：The method of the hydro-thermal reaction is：Powder is shifted To polytetrafluoroethylene (PTFE) in the stainless steel high temperature autoclave of liner, to add the mixture of second alcohol and water as solvent, At 120-180 DEG C, after heating 12-24h, be cooled to room temperature, products therefrom with deionized water and absolute ethyl alcohol be respectively washed 3 times with On, centrifugal filtration, it is dried in vacuo at 50-60 DEG C, obtains Fe-TiO2Microballoon persursor material.
- 7. preparation method according to claim 6, it is characterised in that：The volume ratio of second alcohol and water in solvent is (1-3)： 1。
- 8. preparation method according to claim 3, it is characterised in that：Calcining heat is controlled at 400-600 DEG C, calcining temperature Degree is preferably 450-550 DEG C；Calcination time is controlled in 30min -2h.
- 9. according to the preparation method described in claim 3, it is characterised in that：The nitrogen source of the nitrogen treatment is ammonia.
- 10. according to the preparation method described in claim 9, it is characterised in that：Nitriding temperature is 400-600 DEG C；Nitridation time is 30min-2h。
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