CN109174133B - Molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet and preparation method thereof - Google Patents
Molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet and preparation method thereof Download PDFInfo
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- CN109174133B CN109174133B CN201811093251.3A CN201811093251A CN109174133B CN 109174133 B CN109174133 B CN 109174133B CN 201811093251 A CN201811093251 A CN 201811093251A CN 109174133 B CN109174133 B CN 109174133B
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 114
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 45
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 16
- 238000005516 engineering process Methods 0.000 claims abstract description 15
- 239000011733 molybdenum Substances 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920002492 poly(sulfone) Polymers 0.000 claims description 22
- 238000009987 spinning Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
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- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229920000767 polyaniline Polymers 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 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 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 2
- 150000002751 molybdenum Chemical class 0.000 claims description 2
- 239000010865 sewage Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000003837 high-temperature calcination Methods 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 95
- 239000011521 glass Substances 0.000 description 27
- 238000005303 weighing Methods 0.000 description 18
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 11
- 229960000907 methylthioninium chloride Drugs 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 239000003344 environmental pollutant Substances 0.000 description 8
- 229910052724 xenon Inorganic materials 0.000 description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 7
- 235000018660 ammonium molybdate Nutrition 0.000 description 7
- 239000011609 ammonium molybdate Substances 0.000 description 7
- 229940010552 ammonium molybdate Drugs 0.000 description 7
- 230000000593 degrading effect Effects 0.000 description 7
- 235000015393 sodium molybdate Nutrition 0.000 description 7
- 239000011684 sodium molybdate Substances 0.000 description 7
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 7
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229960005404 sulfamethoxazole Drugs 0.000 description 5
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- 230000001988 toxicity Effects 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Nonwoven Fabrics (AREA)
Abstract
The invention belongs to the field of material preparation and application thereof, and particularly relates to a molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet and a preparation method thereof, wherein a nanofiber is prepared by an electrostatic spinning technology, a molybdenum source and a nitrogen source reagent are added into a titanate solution, a molybdenum-nitrogen co-doped titanium dioxide precursor is deposited on the nanofiber by utilizing in-situ hydrolysis of titanate, and the molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet is prepared by high-temperature calcination; the preparation method is simple and easy for structure regulation and control; the prepared composite nanofiber sheet has a wide photoresponse range, has excellent photocatalytic degradation and conversion effects on organic matters and heavy metals, can remarkably improve the recycling and reusability of the electrospun nanofiber serving as a catalyst carrier, and has a wide application prospect.
Description
Technical Field
The invention belongs to the field of material preparation and application thereof, and particularly relates to a molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet, a preparation method thereof and application thereof in degradation and conversion of environmental pollutants.
Background
The photocatalytic technology uses sunlight to excite a catalyst to generate active species to decompose or convert pollutant molecules, so that the toxicity of pollutants can be effectively reduced, and the photocatalytic technology is widely concerned. Titanium dioxide, as a photocatalyst, has the characteristics of good chemical stability, low price and the like, and is widely used for degrading environmental pollutants, however, the titanium dioxide has low light absorption and utilization rate, is limited to ultraviolet light, and the ultraviolet light only accounts for 5% of sunlight, so that the light energy cannot be effectively utilized; in addition, the titanium dioxide powder catalyst is easy to agglomerate and deactivate due to small particle size, and is easy to run off in practical application, thereby causing secondary pollution. Therefore, a need exists for preparing a novel photocatalyst, which solves the problems of low light absorption efficiency, low activity, difficult recycling and the like of the existing catalyst.
At present, the method for improving the activity of the photocatalyst mainly comprises the steps of doping metal or nonmetal ions and constructing a heterojunction to widen the light absorption range of the catalyst and reduce the band gap width, so that the catalytic activity of the catalyst is improved. The electrostatic spinning nanofiber has the advantages of large specific surface area, easiness in modification and simple and controllable preparation process, and is widely applied to the aspect of environmental pollutant treatment. Moreover, the composite nano-catalyst can be prepared by chemical grafting, blending, heat treatment and the like. In addition, the electrospun nanofiber can also be used as a carrier of a plurality of high-efficiency catalysts, thereby improving the recycling performance of the powder material, avoiding material loss and reducing secondary pollution. The nano-fiber prepared by the electrostatic spinning technology can be carbonized through high-temperature calcination, and the carbonized nano-fiber has the characteristics of good conductivity, light weight, high mechanical strength and the like, so that the nano-fiber becomes a good carrier of the photocatalyst. In conclusion, the electrostatic spinning nano-fiber is used as a carrier, and the problems of improving the activity and recycling of the powder catalyst by combining ion doping are significant. At present, although a catalyst of titanium dioxide loaded on nano fibers is reported in a patent, the synthesis method is complicated, uneven and easy to agglomerate, the fiber matrix is too thick, and the conductivity is not good, so that the catalytic efficiency is not high. The invention improves the thickness and conductivity of the nano-fiber through two-step synthesis of hydrolysis and calcination, and simultaneously improves the activity of the titanium dioxide catalyst through metal and nonmetal ion codoping.
Disclosure of Invention
The invention solves the technical problems of low catalytic efficiency, easy agglomeration and inactivation and difficult recovery of a photocatalyst in the prior art, and provides a molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet and a preparation method thereof.
In order to solve the problems, the technical scheme of the invention is as follows:
a preparation method of a molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet comprises the following steps:
and 3, placing the nanofiber prepared in the step 2 into the solution C obtained in the step 1, soaking for 1-24 hours, drying, and calcining for 2-16 hours at the high temperature of 450-600 ℃ to obtain the molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet.
Preferably, in step 1, the titanate is any one of n-butyl titanate, isopropyl titanate and tetraethyl titanate; the organic solvent is any one of ethanol, ethylene glycol and isopropanol; the molybdenum source reagent is a soluble molybdenum salt, such as sodium molybdate, ammonium molybdate, zinc molybdate; the nitrogen source reagent is any one of ammonia water, urea and nitric acid.
Preferably, in step 2, the high molecular polymer is any one of polysulfone, polyvinyl alcohol and polyaniline.
Preferably, in the step 2, the mass fraction of the high molecular polymer solution is 8% to 15%.
Preferably, in step 2, the conditions of the high-voltage electrostatic spinning are as follows: the spinning voltage is 10-30 kV, the flow rate of spinning liquid is 0.5-2.0 ml/h, and the collection distance is 13-22 cm.
Preferably, in step 1, the volume fraction of titanate in the solution A is 5-20%; the mass concentration of the molybdenum source reagent in the solution B is 10-60 g/L; in the step 1, the volume fraction of the added nitrogen source reagent in the solution B is 1-10%.
Preferably, in step 3, the addition amount of the nanofibers is: 1-5g of nanofibers per 50ml of solution C was added.
The molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet can be used for removing pollutants in a water environment. The contaminants include organic contaminants or heavy metal contaminants.
Compared with the prior art, the invention has the advantages that,
the invention provides a preparation method of a molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet, which comprises the steps of taking high-molecular polymer nanofiber as a carrier, carrying out in-situ hydrolysis growth on a titanium dioxide precursor, forming molybdenum-nitrogen co-doped titanium dioxide nanorods through a high-temperature calcination one-step method, uniformly distributing the molybdenum-nitrogen co-doped titanium dioxide nanorods on the nanofiber, and compositely preparing the nanofiber sheet capable of efficiently degrading and converting water pollutants;
compared with the common catalytic material, the composite nanofiber sheet prepared by the invention has the advantages of obviously enhanced absorption performance in a visible light region, high electron hole separation efficiency and high conversion rate.
Compared with most of powder catalysts, the composite nanofiber sheet prepared by the invention solves the problems that the existing powder catalyst is easy to agglomerate and deactivate and difficult to recover, and can be repeatedly used.
The nano-fiber is calcined at high temperature and then used as a catalyst carrier, so that the conductivity is good, the electron transmission can be promoted, the occupied volume and mass of the carrier are small, and the use is convenient.
Drawings
Fig. 1 is a diagram of a composite nanofiber sheet according to example 2 of the present invention;
FIG. 2 is a scanning electron micrograph of a composite nanofiber sheet according to example 2 of the present invention;
FIG. 3 is a graph showing the effect of degrading methylene blue by the composite nanofiber sheet prepared in example 2 of the present invention;
FIG. 4 is a graph showing the effect of the composite nanofiber sheet prepared in example 2 of the present invention in degrading sulfamethoxazole;
FIG. 5 is a graph showing the effect of degrading bisphenol A by the composite nanofiber sheet prepared in example 2 of the present invention;
FIG. 6 is a graph of the reuse performance of composite nanofiber sheets prepared in example 2 of the present invention;
FIG. 7 is a solid UV ray of composite nanofiber sheet (A) prepared in example 2 of the present invention and commercial titanium dioxide (B)
Diffuse reflectance spectrum contrast map;
FIG. 8 is a full-spectrum X-ray electron energy spectrum scan of the composite nanofiber sheet prepared in example 2 of the present invention;
FIG. 9 is the diagram of the morphological analysis of molybdenum element in the X-ray electron spectrum of the composite nanofiber sheet prepared in example 2 of the present invention;
FIG. 10 is the nitrogen element morphological analysis chart of the X-ray electron energy spectrum of the composite nanofiber sheet prepared in example 2 of the present invention.
Detailed Description
Example 1:
the preparation method of the molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet comprises the following steps:
1) dissolving 2mL of n-butyl titanate in 40mL of isopropanol, and stirring uniformly to obtain a solution A; weighing 0.1g of sodium molybdate, adding the sodium molybdate into 10mL of aqueous solution, adding 0.1mL of nitric acid, and uniformly mixing to obtain solution B; slowly adding the solution B into the solution A and continuously stirring to obtain a solution C;
2) preparing 8% polysulfone solution, filling the polysulfone solution into a glass injector, fixing the glass injector on an injection pump of an electrostatic spinning device, connecting a negative electrode of a spinning machine with a collecting plate, connecting a positive electrode of the spinning machine with the glass injector, adjusting the voltage to 10kv, adjusting the distance between the positive electrode and the negative electrode to 13cm, and adjusting the flow rate to 0.5mL/h, and preparing polysulfone nano-fibers by using an electrostatic spinning technology;
3) weighing 1g of polysulfone nanofiber, placing the polysulfone nanofiber in 50mL of solution C, soaking for 1 hour, taking out, drying in an oven at 80 ℃, then placing in a muffle furnace, and calcining at 450 ℃ for 2 hours.
Example 2:
the preparation method of the molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet comprises the following steps:
1) dissolving 4mL of n-butyl titanate in 40mL of isopropanol, and stirring uniformly to obtain a solution A; weighing 0.3g of sodium molybdate, adding the sodium molybdate into 10mL of aqueous solution, adding 0.5mL of nitric acid, and uniformly mixing to obtain solution B; slowly adding the solution B into the solution A, and continuously stirring to obtain a solution C;
2) preparing 12% polysulfone solution, filling the polysulfone solution into a glass injector, fixing the glass injector on an injection pump of an electrostatic spinning device, connecting a negative electrode of a spinning machine with a collecting plate, connecting a positive electrode of the spinning machine with the glass injector, adjusting the voltage to be 15kv, adjusting the distance between the positive electrode and the negative electrode to be 16cm, and adjusting the flow rate to be 1.0mL/h, and preparing polysulfone nano-fibers by using an electrostatic spinning technology;
3) weighing 2.5g of polysulfone nano-fiber, placing the polysulfone nano-fiber in 50mL of solution C, soaking for 8 hours, taking out, drying in an oven at 80 ℃, placing in a muffle furnace, and calcining at 500 ℃ for 4 hours.
Example 3
The preparation method of the molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet comprises the following steps:
1) dissolving 8mL of n-butyl titanate in 40mL of isopropanol, and stirring uniformly to obtain a solution A; weighing 0.6g of sodium molybdate, adding the sodium molybdate into 10mL of aqueous solution, adding 1.0mL of nitric acid, and uniformly mixing to obtain solution B; slowly adding the solution B into the solution A and continuously stirring to obtain a solution C;
2) preparing 15% polysulfone solution, filling the 15% polysulfone solution into a glass injector, fixing the glass injector on an injection pump of an electrostatic spinning device, connecting a negative electrode of a spinning machine with a collecting plate, connecting a positive electrode of the spinning machine with the glass injector, adjusting the voltage to be 30kv, adjusting the distance between the positive electrode and the negative electrode to be 22cm, and adjusting the flow rate to be 2.0mL/h, and preparing polysulfone nano-fibers by using an electrostatic spinning technology;
3) weighing 5g of polysulfone nanofibers, placing the polysulfone nanofibers in 50mL of solution C, soaking for 24 hours, taking out the polysulfone nanofibers, drying the polysulfone nanofibers in an oven at 80 ℃, then placing the polysulfone nanofibers in a muffle furnace, and calcining the polysulfone nanofibers at 600 ℃ for 16 hours.
Example 4
The preparation method of the molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet comprises the following steps:
1) dissolving 2mL of tetraethyl titanate in 40mL of ethanol, and stirring uniformly to obtain a solution A; weighing 0.1g of ammonium molybdate, adding the ammonium molybdate into 10mL of aqueous solution, adding 0.1mL of urea, and uniformly mixing to obtain solution B; slowly adding the solution B into the solution A and continuously stirring to obtain solution C;
2) preparing 8% polyaniline solution, loading the solution into a glass injector, fixing the glass injector on an injection pump of an electrostatic spinning device, connecting a negative electrode of a spinning machine with a collecting plate, connecting a positive electrode of the spinning machine with the glass injector, adjusting the voltage to 10kv, adjusting the distance between the positive electrode and the negative electrode to 13cm, and adjusting the flow rate to 0.5mL/h, and preparing polyaniline nano-fibers by using an electrostatic spinning technology;
3) weighing 1g of polyaniline nanofiber, placing the polyaniline nanofiber in 50mL of solution C, soaking for 1 hour, taking out, drying in an oven at 80 ℃, then placing in a muffle furnace, and calcining at 450 ℃ for 2 hours.
Example 5
The preparation method of the molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet comprises the following steps:
1) dissolving 4mL of tetraethyl titanate in 40mL of ethanol, and stirring uniformly to obtain a solution A; placing the mixture into a magnetic stirrer for stirring, weighing 0.3g of ammonium molybdate, adding the ammonium molybdate into 10mL of aqueous solution, adding 0.5mL of urea, and uniformly mixing to obtain solution B; slowly adding the solution B into the solution A and continuously stirring to obtain a solution C;
2) preparing a 12% polyaniline solution, filling the solution into a glass injector, fixing the glass injector on an injection pump of an electrostatic spinning device, connecting a negative electrode of a spinning machine with a collecting plate, connecting a positive electrode of the spinning machine with the glass injector, adjusting the voltage to be 15kv, adjusting the distance between the positive electrode and the negative electrode to be 16cm, and adjusting the flow rate to be 1.0mL/h, and preparing polyaniline nanofibers by using an electrostatic spinning technology;
3) weighing 2.5g of polyaniline nano-fiber, placing the polyaniline nano-fiber in 50mL of solution C, soaking for 8 hours, taking out, drying in an oven at 80 ℃, placing in a muffle furnace, and calcining at 500 ℃ for 4 hours.
Example 6
The preparation method of the molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet comprises the following steps:
1) dissolving 8mL of tetraethyl titanate in 40m of ethanol, and stirring uniformly to obtain a solution A; weighing 0.6g of ammonium molybdate, adding the ammonium molybdate into 10mL of aqueous solution, adding 1.0mL of urea, and uniformly mixing to obtain solution B; slowly adding the solution B into the solution A and continuously stirring to obtain a solution C;
2) preparing a 15% polyaniline solution, filling the solution into a glass injector, fixing the glass injector on an injection pump of an electrostatic spinning device, connecting a negative electrode of a spinning machine with a collecting plate, connecting a positive electrode of the spinning machine with the glass injector, adjusting the voltage to be 30kv, adjusting the distance between the positive electrode and the negative electrode to be 22cm, and adjusting the flow rate to be 2.0mL/h, and preparing polyaniline nanofibers by using an electrostatic spinning technology;
3) weighing 5g of polyaniline nano-fiber, placing the polyaniline nano-fiber in 50mL of solution C, soaking for 24 hours, taking out, drying in an oven at 80 ℃, placing in a muffle furnace, and calcining at 600 ℃ for 16 hours.
Example 7
The preparation method of the molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet comprises the following steps:
1) dissolving 2mL of isopropyl titanate in 40mL of ethylene glycol, and stirring uniformly to obtain a solution A; weighing 0.1g of zinc molybdate, adding the zinc molybdate into 10mL of aqueous solution, adding 0.1mL of ammonia water, and uniformly mixing to obtain solution B; slowly adding the solution B into the solution A and continuously stirring to obtain a solution C;
2) preparing 8% polyvinyl alcohol solution, loading the polyvinyl alcohol solution into a glass injector, fixing the glass injector on an injection pump of an electrostatic spinning device, connecting a negative electrode of a spinning machine with a collecting plate, connecting a positive electrode of the spinning machine with the glass injector, adjusting the voltage to be 10kv, adjusting the distance between the positive electrode and the negative electrode to be 13cm, and adjusting the flow rate to be 0.5mL/h, and preparing polyvinyl alcohol nanofibers by using an electrostatic spinning technology;
3) weighing 1g of polysulfone nanofiber polyvinyl alcohol nanofiber in 50mL of solution C, soaking for 1 hour, taking out, drying in an oven at 80 ℃, then placing in a muffle furnace, and calcining at 450 ℃ for 2 hours.
Example 8
The preparation method of the molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet comprises the following steps:
1) dissolving 4mL of isopropyl titanate in 40mL of ethylene glycol, and stirring uniformly to obtain a solution A; weighing 0.3g of zinc molybdate, adding the zinc molybdate into 10mL of aqueous solution, adding 0.5mL of ammonia water, and uniformly mixing to obtain solution B; slowly adding the solution B into the solution A and continuously stirring to obtain a solution C;
2) preparing a 12% polyvinyl alcohol solution, loading the polyvinyl alcohol solution into a glass injector, fixing the glass injector on an injection pump of an electrostatic spinning device, connecting a negative electrode of a spinning machine with a collecting plate, connecting a positive electrode of the spinning machine with the glass injector, adjusting the voltage to be 15kv, adjusting the distance between the positive electrode and the negative electrode to be 16cm, and adjusting the flow rate to be 1.0mL/h, and preparing polyvinyl alcohol nanofibers by using an electrostatic spinning technology;
3) weighing 2.5g of polyvinyl alcohol nano-fiber in 50mL of solution C, soaking for 8 hours, taking out, drying in an oven at 80 ℃, then placing in a muffle furnace, and calcining at 500 ℃ for 4 hours.
Example 9
The preparation method of the molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet comprises the following steps:
1) dissolving 8mL of isopropyl titanate in 40m of ethylene glycol, and stirring uniformly to obtain a solution A; weighing 0.6g of zinc molybdate, adding the zinc molybdate into 10mL of aqueous solution, adding 1.0mL of ammonia water, and uniformly mixing to obtain solution B; slowly adding the solution B into the solution A and continuously stirring to obtain a solution C;
2) preparing 15% polyvinyl alcohol solution, loading the 15% polyvinyl alcohol solution into a glass injector, fixing the glass injector on an injection pump of an electrostatic spinning device, connecting a negative electrode of a spinning machine with a collecting plate, connecting a positive electrode of the spinning machine with the glass injector, adjusting the voltage to be 30kv, adjusting the distance between the positive electrode and the negative electrode to be 22cm, and adjusting the flow rate to be 2.0mL/h, and preparing polyvinyl alcohol nanofibers by using an electrostatic spinning technology;
3) weighing 5g of polyvinyl alcohol nanofiber, placing the polyvinyl alcohol nanofiber in 50mL of solution C, soaking for 24 hours, taking out, drying in an oven at 80 ℃, then placing in a muffle furnace, and calcining at 600 ℃ for 16 hours.
Example 10
15mg of the composite nanofiber sheet prepared in example 2 was placed in 50mL of methylene blue solution with a concentration of 30mg/L, pre-adsorbed for one hour under a dark condition, a 500w xenon lamp was turned on to perform illumination, samples were taken at intervals, and the absorbance was measured at a wavelength of 664nm with an ultraviolet spectrophotometer. The degradation curve is shown in fig. 3, and it can be seen from the graph that the prepared composite nanofiber sheet can rapidly and efficiently degrade methylene blue. Wherein the degradation rate is (A)0-A)/A0,A0The initial peak area of the methylene blue solution is shown, and A is the peak area of the methylene blue solution after the composite nanofiber sheet is treated.
Example 11
25mg of the composite nanofiber sheet prepared in example 2 was placed in 50mL of sulfamethoxazole solution with a concentration of 20mg/L, pre-adsorbed for 30 minutes in the dark, a 500w xenon lamp was turned on to perform illumination, samples were taken at intervals, and the peak area was measured at a wavelength of 276nm by liquid chromatography. The degradation curve is shown in FIG. 4, from which it can be seen that the prepared compositesThe nano-fiber sheet can be used for quickly and efficiently degrading sulfamethoxazole. Wherein the degradation rate is (A)0-A)/A0,A0The initial peak area of sulfamethoxazole is shown, and A shows the peak area of sulfamethoxazole remained after the composite nanofiber sheet is treated.
Example 12
25mg of the composite nanofiber sheet prepared in example 2 was placed in 50mL of a bisphenol A solution having a concentration of 20mg/L, pre-adsorbed for 30 minutes in the dark, a 500w xenon lamp was turned on to perform illumination, samples were taken at intervals, and the peak area was measured at a wavelength of 276nm by liquid chromatography. The degradation curve is shown in fig. 5, and it can be seen from the graph that the prepared composite nanofiber sheet can rapidly and efficiently degrade bisphenol a. Wherein the degradation rate is (A)0-A)/A0,A0Showing the initial peak area of bisphenol a and a showing the peak area of bisphenol a remaining after treatment of the composite nanofiber sheet.
Example 13
15mg of the composite nanofiber sheet prepared in example 2 was placed in 50mL of a methylene blue solution with a concentration of 30mg/L, pre-adsorbed for one hour under a dark condition, a 500w xenon lamp was turned on to perform illumination for three hours, and the absorbance was measured at a wavelength of 664nm with an ultraviolet spectrophotometer. Taking out with tweezers, washing with ethanol, oven drying, and repeating the above steps. As shown in fig. 6, after 5 times of recycling, the catalytic degradation effect is not significantly reduced and is maintained within 10%, which indicates that the composite nanofiber sheet prepared by the invention has good recycling performance and application prospect.
Example 14
The molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet prepared in the examples 1 and 3 to 9 is placed in 50mL methylene blue solution with the concentration of 30mg/L, pre-adsorbed for one hour under the dark condition, a 500w xenon lamp is turned on to illuminate for three hours, an ultraviolet spectrophotometer is used for measuring absorbance at the wavelength of 664nm, and the calculated removal rate is over 90 percent.
Example 15
The molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheets prepared in examples 1 to 10 were placed in a container containing Cr6+Pre-adsorbing for one hour under the conditions of middle and darkAnd starting a 500w xenon lamp for illumination for three hours, wherein the result shows that Cr is6+Is reduced into Cr3+。
Example 16
Selecting the molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet prepared in the example 2 to perform X-ray electron energy spectrum analysis on the doping condition of molybdenum and nitrogen, wherein the result is shown in fig. 8, C, N, O, Ti and Mo contained in the molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet prepared in the example 2 are detected, which indicates that the molybdenum and the nitrogen are successfully doped into a titanium dioxide crystal lattice, and the molybdenum and the nitrogen doped in the material are subjected to peak separation treatment respectively in fig. 9 and 10, and the result indicates that the doped molybdenum mainly exists in a hexavalent molybdenum form; while nitrogen exists mainly in the form of C-N, β -N and γ -N. The ionic radius of hexavalent molybdenum is similar to that of tetravalent titanium, so that the hexavalent molybdenum can enter the crystal lattice of titanium dioxide, and the beta-N can improve the visible light absorption and photocatalytic activity of the titanium dioxide.
With the combination of the embodiments 1-16, the composite nanofiber sheet prepared by the preparation method provided by the invention can be used for rapidly and efficiently degrading and converting various pollutants in a water environment, and the conversion rate is high. The preparation method provided by the invention is simple and easy to implement, has low energy consumption, and has wide application prospect in the aspect of pollutant conversion and degradation in water.
Comparative example 1
15mg of the composite nanofiber sheet prepared in example 2 and commercial titanium dioxide (P25) were placed in 50mL of methylene blue solution with a concentration of 30mg/L, respectively, and pre-adsorbed for one hour under dark conditions, a 500w xenon lamp was turned on to illuminate for three hours, and the content of the remaining total organic carbon in the solution was determined. The mineralization rate of the composite nanofiber sheet prepared by the method disclosed by the invention on methylene blue can reach 79.8%, while commercial titanium dioxide (P25) is only 45.3%.
Comparative example 2
Two composite nanofiber sheets were prepared separately as in example 2: one part was identical to example 2, and the other part was not calcined at high temperature in a muffle furnace, 15mg of each of which was weighed out and placed in 50mL of a methylene blue solution with a concentration of 30mg/L, and the solution was pre-adsorbed for one hour in the dark, and a 500w xenon lamp was turned on to illuminate for three hours, and the results showed that: the mineralization rate of the methylene blue degraded by the composite nanofiber sheet which is not calcined at high temperature is only 31.2%.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and all equivalent substitutions or substitutions made on the above-mentioned embodiments are included in the scope of the present invention.
Claims (8)
1. The preparation method of the molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet is characterized by comprising the following steps of:
step 1, dissolving titanate in an organic solvent to prepare a solution A; dissolving a molybdenum source and a nitrogen source reagent in water to prepare a solution B; slowly adding the solution B into the solution A and continuously stirring to obtain a solution C;
step 2, preparing a high molecular polymer solution, and preparing the nano fiber by using a high-voltage electrostatic spinning technology;
step 3, placing the nanofiber prepared in the step 2 in the solution C obtained in the step 1, soaking for 1-24 hours, drying, and calcining for 2-16 hours at a high temperature of 450-600 ℃ to obtain the molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet;
in the step 1, the volume fraction of titanate in the solution A is 5-20%; the mass concentration of the molybdenum source reagent in the solution B is 10-60 g/L; the volume fraction of the added nitrogen source reagent in the solution B is 1-10%.
2. The method for preparing the molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet as claimed in claim 1, wherein in the step 1, the titanate is any one of n-butyl titanate, isopropyl titanate and tetraethyl titanate; the organic solvent is any one of ethanol, ethylene glycol and isopropanol; the molybdenum source reagent is soluble molybdenum salt; the nitrogen source reagent is any one of ammonia water, urea and nitric acid.
3. The method for preparing the molybdenum-nitrogen-codoped titanium dioxide composite nanofiber sheet as claimed in claim 1, wherein in the step 2, the high molecular polymer is any one of polysulfone, polyvinyl alcohol and polyaniline.
4. The method for preparing the molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet as claimed in claim 1, wherein in the step 2, the mass fraction of the high molecular polymer solution is 8% -15%.
5. The method for preparing the molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet as claimed in claim 1, wherein in the step 2, the conditions of the high-voltage electrostatic spinning are as follows: the spinning voltage is 10-30 kV, the flow rate of spinning liquid is 0.5-2.0 ml/h, and the collection distance is 13-22 cm.
6. The method for preparing the molybdenum-nitrogen co-doped titanium dioxide composite nanofiber sheet as claimed in claim 1, wherein in the step 3, the addition amount of the nanofibers is as follows: 1-5g of nanofibers per 50ml of solution C was added.
7. The molybdenum nitrogen-codoped titanium dioxide composite nanofiber sheet prepared by the method as claimed in any one of claims 1 to 6.
8. The use of the molybdenum nitrogen-co-doped titanium dioxide composite nanofiber sheet as claimed in claim 7 in sewage treatment.
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| CN105013461A (en) * | 2015-06-30 | 2015-11-04 | 宁波工程学院 | Application of N-doped TiO2 nano fiber in high-efficiency visible light photocatalyst |
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| CN105013461A (en) * | 2015-06-30 | 2015-11-04 | 宁波工程学院 | Application of N-doped TiO2 nano fiber in high-efficiency visible light photocatalyst |
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| Characterization and mechanism analysis of Mo-N-co-doped TiO2 nano-photocatalyst and its enhanced visible activity;Xiuwen Cheng et al.;《Journal of Colloid and Interface Science》;20111206;第372卷;第1-5页 * |
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