CN109589996B - TiO 2 2 Base/two-dimensional material nano composite photocatalytic fiber membrane and preparation method thereof - Google Patents
TiO 2 2 Base/two-dimensional material nano composite photocatalytic fiber membrane and preparation method thereof Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 91
- 239000000463 material Substances 0.000 title claims abstract description 85
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 85
- 239000012528 membrane Substances 0.000 title claims abstract description 64
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000005516 engineering process Methods 0.000 claims abstract description 20
- 239000011324 bead Substances 0.000 claims abstract description 9
- 238000001514 detection method Methods 0.000 claims abstract description 9
- 238000004146 energy storage Methods 0.000 claims abstract description 9
- 238000001782 photodegradation Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 17
- 238000007639 printing Methods 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 13
- 238000012986 modification Methods 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000013538 functional additive Substances 0.000 claims description 6
- 230000003287 optical effect Effects 0.000 claims description 6
- 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 6
- 125000000524 functional group Chemical group 0.000 claims description 5
- -1 graphite alkyne Chemical class 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000002159 nanocrystal Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical class [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 239000008204 material by function Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 abstract description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
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- 238000007306 functionalization reaction Methods 0.000 description 5
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 239000003570 air Substances 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
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- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 1
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- 230000000593 degrading effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 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 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
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Images
Classifications
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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
- 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
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- B01J35/39—
-
- B01J35/59—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention provides a TiO 2 A base/two-dimensional material nano composite photocatalytic fiber membrane and a preparation method thereof, wherein a two-dimensional material wraps TiO 2 Based on the precursor material, the precursor material is prepared into a bead string-shaped or pea-shaped nano composite fiber structure film by a jet forming technology. The photocatalytic fiber membrane has the advantages of high photocatalytic activity, good toughness and repeated use, can realize rapid molding on the surface of a rigid, flexible and curved substrate and preparation of complex patterns and multifunctional devices, and can meet the application requirements of energy environment fields such as photodegradation, photocatalytic energy storage and photo detection and civilian fields such as wearable clothes.
Description
Technical Field
The invention belongs to the technical field of preparation and application of nano composite materials and photocatalytic devices, and particularly relates to a TiO (titanium dioxide) photocatalyst 2 A base/two-dimensional material nano composite photocatalytic fiber membrane and a preparation method thereof.
Background
Titanium dioxide as oneThe wide band gap semiconductor material has the advantages of excellent photocatalytic performance, low cost, easy preparation, no toxicity, high chemical stability, etc. and is widely applied in energy storage, environment protection, biological detection and other fields. TiO prepared by high-voltage electrostatic jet forming technology 2 Based on a nanofiber membrane of TiO 2 The size of the base material is reduced to a nanoscale size, and the effects of large specific surface area and small size of the nano material are exerted; meanwhile, the network structure based on the carbon fiber cross-linked texture further widens TiO 2 The properties and range of applications of the base material. Compared with nano-fiber, the large specific surface characteristic of nano-particles can provide more active sites, and TiO uniformly adhered to the surface can be obtained by selecting a titanium source and a polymer and improving a high-voltage electrostatic jet forming process 2 Nanofiber membranes of base materials. However, the fiber film prepared by the high-voltage electrostatic jet forming process has the problems of orientation distribution, large strength difference in different directions and incapability of fundamentally solving the problem by only depending on the improvement of the process, which is limited by the limitation of the forming process. If a material with good carrier transport property can be used to wrap TiO 2 The base material is prepared into the bead string-shaped or pea-shaped nanometer composite fiber structure film through a jet forming technology, and the existence of the bead string-shaped or pea-shaped structure can obviously increase the external force required by fiber deformation and even breakage, so that good toughness and high catalytic activity can be obtained simultaneously. The two-dimensional material represented by graphene has excellent carrier mobility, large specific surface area, good electrical conductivity and thermal conductivity, and abundant functional groups and good hydrophilic property, and is more beneficial to TiO 2 Provides more active sites and facilitates the transfer of photogenerated carriers. Further, through the optimization of the structure, the rapid forming on the surface of a rigid, flexible and curved substrate and the preparation of complex patterns and multifunctional junction devices can be realized, and the application requirements of the energy environment fields such as photodegradation, photocatalytic energy storage and optical detection and the civil fields such as wearable clothes are met. Thus, a TiO has been developed 2 The base/two-dimensional material nano composite photocatalytic fiber membrane is particularly important.
Disclosure of Invention
Based on the technical problems existing in the background technology, the invention aims to provide a TiO 2 A base/two-dimensional material nano composite photocatalytic fiber membrane, which wraps TiO with a two-dimensional material 2 The precursor material is prepared into the bead string-shaped or pea-shaped nano composite fiber structure film by the jet forming technology, has the advantages of high photocatalytic activity, good toughness and repeated use, can realize the rapid forming of the surface of a rigid, flexible and curved substrate and the preparation of complex patterns and multifunctional junction devices, and can meet the application requirements of energy environment fields such as photodegradation, photocatalytic energy storage, optical detection and the like and civil fields such as wearable clothes and the like. The specific technical scheme is as follows:
TiO 2 2 The preparation method of the base/two-dimensional material nano composite photocatalytic fiber membrane is characterized by comprising the following steps of:
(1) Carrying out surface modification treatment on the two-dimensional material to obtain a two-dimensional material with a surface rich in functional groups;
(2)TiO 2 preparing a base/two-dimensional material precursor solution;
(3) Printing TiO on the surface of a substrate by adopting a high-voltage electrostatic jet forming technology 2 A base/two-dimensional material nano composite photocatalytic fiber membrane;
(4) Aging treatment and surface modification under a low-temperature condition;
(5) Carbonizing under high temperature and functionalizing.
Optionally, in the preparation method of the photocatalytic fiber membrane, the surface modification treatment of the two-dimensional material is performed for 30-150min by using a modification solution, then the two-dimensional material is cleaned and dried, and then the two-dimensional material is treated for 10-120min by using a plasma or ultraviolet ozone device;
the modifying solution comprises H 2 S、NH 3 ·H 2 O、KMnO 4 One or more of aqueous solutions.
Optionally, in the preparation method of the photocatalytic fiber membrane, tiO 2 The base/two-dimensional material precursor solution comprises the following components:
the TiO is 2 The base precursor consists of a titanium source and a functional additive material;
the titanium source comprises one or more of titanium isopropoxide, titanium tetrachloride, tetrabutyl titanate and titanium sulfate;
the functional additive material comprises inorganic salt containing B, N, sn, mn and other elements, znO nanocrystal and SnO 2 One or more of nanocrystalline, carbon quantum dots, cdSe quantum dots and the like;
the polymer comprises one or more of PVP, PAN, PMMA, PVAc and PLA;
the two-dimensional material comprises graphene, graphene oxide, reduced graphene oxide, graphite alkyne, boron nitride, black phosphorus and MoS 2 One or more of transition metal chalcogenide compounds;
the solvent comprises one or more of DMF, DMSO, isopropanol, toluene, chlorobenzene, acetic acid and other solutions;
optionally, in the preparation method of the photocatalytic fiber membrane, the voltage adopted by the high-voltage electrostatic jet forming technology is 1-30kV; the aperture of the nozzle is 1-50 μm;
optionally, in the preparation method of the photocatalytic fiber membrane, the aging treatment under the low-temperature condition is to place the nano composite fiber membrane in a temperature and humidity box with the temperature of 20-70 ℃ and the humidity of 20-80% for storage for 2-48h, then place the nano composite fiber membrane in a forced air drying box with the temperature of 200-300 ℃ for storage for 2-8h, and finally use plasma or ultraviolet ozone equipment for treatment for 10-120min;
optionally, in the preparation method of the photocatalytic fiber membrane, the carbonization and the functionalization treatment under the high-temperature condition adopt an atmosphere furnace sintering mode, and the carbonization and the functionalization treatment are respectively carried out under the atmosphere of air, argon, mixed gas and the like at the temperature of 500-900 DEG CMiddle heat preservation 2-6h、1-3h、2-8h。
The mixed atmosphere is composed of argon, oxygen and H 2 S and ammonia gas or a plurality of the S and the ammonia gas;
optionally, in the preparation method of the photocatalytic fiber membrane, rapid prototyping and printing can be directly performed on the surface of a rigid, flexible and curved substrate by adopting a high-voltage electrostatic jet forming technology;
optionally, in the preparation method of the photocatalytic fiber membrane, after the surface of the substrate is covered with the patterned template, the high-voltage electrostatic jet forming technology is used for printing a complex pattern;
optionally, in the preparation method of the photocatalytic fiber film, the surface of the substrate can be printed with the nano composite fiber film, and then other functional materials are printed to obtain the multifunctional junction device;
optionally, the photocatalytic fiber membrane can meet application requirements of energy environment fields such as photodegradation, photocatalytic energy storage and photo detection and civilian fields such as wearable clothes.
The beneficial effects of the invention are: by designing and preparing a two-dimensional material wrapped TiO 2 Based on the precursor material, the precursor material is prepared into a bead string-shaped or pea-shaped nano composite fiber structure film by a jet forming technology. The photocatalytic fiber film has the advantages of high photocatalytic activity, good toughness and repeated use, can realize rapid molding on the surface of a rigid, flexible and curved substrate and preparation of complex patterns and multifunctional devices, and can meet the application requirements of energy environment fields such as photodegradation, photocatalytic energy storage and optical detection and civil fields such as wearable clothes.
Drawings
FIG. 1 shows TiO of the present invention 2 A flow chart of the preparation of the base/two-dimensional material nano composite photocatalytic fiber membrane.
FIGS. 2 (a) -2 (b) are SEM images of photocatalytic fiber membranes used in examples of the present invention and comparative examples.
FIGS. 3 (a) -3 (b) are TEM images of photocatalytic fiber membranes used in examples of the present invention and comparative examples.
FIG. 4 is a graph showing the blue light degradation efficiency of methylene of photocatalytic fiber films used in examples of the present invention and comparative examples.
FIG. 5 is a graph showing mechanical properties of photocatalytic fiber membranes used in examples of the present invention and comparative examples.
FIGS. 6 (a) -6 (e) are schematic diagrams of different substrate structures to which the present invention can be applied.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings and examples, and it is to be understood that the described examples are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without any creative efforts shall fall within the protection scope of the present invention.
In order to solve the problems of orientation distribution, large strength difference in different directions and the like of a fiber film prepared by a high-pressure electrostatic jet forming process in the prior art, the invention provides a TiO 2 A base/two-dimensional material nano composite photocatalytic fiber membrane, tiO is wrapped by a two-dimensional material 2 Based on the precursor material, the precursor material is prepared into a bead string-shaped or pea-shaped nano composite fiber structure film by a jet forming technology. The photocatalytic fiber film has the advantages of high photocatalytic activity, good toughness and repeated use, can realize rapid molding on the surface of a rigid, flexible and curved substrate and preparation of complex patterns and multifunctional devices, and can meet the application requirements of energy environment fields such as photodegradation, photocatalytic energy storage and optical detection and civil fields such as wearable clothes.
The following TiO is provided in general for the embodiments of the invention 2 The base/two-dimensional material nano composite photocatalytic fiber membrane is illustrated.
FIG. 1 shows TiO of the present invention 2 A flow chart of the preparation of the base/two-dimensional material nano composite photocatalytic fiber membrane.
FIGS. 2 (a) -2 (b) are SEM images of photocatalytic fiber membranes used in examples of the present invention and comparative examples.
Wherein FIG. 2 (a) is TiO 2 SEM picture of base/two-dimensional material nano composite photocatalytic fiber membrane, and FIG. 2 (b) is TiO 2 SEM of the base nano photocatalytic fiber membrane;
FIGS. 3 (a) -3 (b) are TEM images of photocatalytic fiber membranes used in examples of the present invention and comparative examples.
Wherein FIG. 3 (a) is TiO 2 TEM image of base/two-dimensional material nano composite photocatalytic fiber membrane, and FIG. 3 (b) is TiO 2 TEM of the base nano photocatalytic fiber film;
FIG. 4 is a graph showing the blue light degradation efficiency of methylene of photocatalytic fiber films used in examples of the present invention and comparative examples.
FIG. 5 is a graph showing mechanical properties of photocatalytic fiber membranes used in examples of the present invention and comparative examples.
FIGS. 6 (a) -6 (e) are schematic diagrams of different substrate structures to which the present invention can be applied.
Wherein fig. 6 (a) is a rigid substrate, fig. 6 (b) is a flexible substrate, fig. 6 (c) is a curved substrate, and fig. 6 (d) is a patterned printing of a photocatalytic fiber film; fig. 6 (e) is a multifunctional junction device structure containing a photocatalytic fiber membrane.
As shown in figure 1, the TiO provided by the invention 2 The preparation flow chart of the base/two-dimensional material nano composite photocatalytic fiber membrane comprises the following steps:
(1) Carrying out surface modification treatment on the two-dimensional material to obtain a two-dimensional material with a surface rich in functional groups;
(2)TiO 2 preparing a base/two-dimensional material precursor solution;
(3) Printing TiO on a substrate by high-voltage electrostatic jet forming technology 2 A base/two-dimensional material nano composite photocatalytic fiber membrane;
(4) Aging treatment and surface modification under a low-temperature condition;
(5) Carbonizing and functionalizing under high temperature.
Specifically, the method comprises the following steps:
the surface modification treatment of the two-dimensional material is carried out by treating with a modification solution, cleaning, drying and then treating with plasma or ultraviolet ozone equipment, so that the two-dimensional material with high activity and rich functional groups can be obtained, and TiO is favorably treated 2 Rich attachment of the base precursor material; the modifying solution comprises H 2 S、NH 3 ·H 2 O、KMnO 4 One or more of aqueous solutions.
The TiO is 2 The base/two-dimensional material precursor solution comprises the following components:
the TiO is 2 The base precursor consists of a titanium source and a functional additive material; the titanium source comprises one or more of titanium isopropoxide, titanium tetrachloride, tetrabutyl titanate and titanium sulfate; the functional additive material comprises inorganic salt containing B, N, sn, mn and other elements, znO nanocrystal and SnO 2 One or more of nanocrystals, carbon quantum dots, cdSe quantum dots, etc.; the polymer is one or more of PVP, PAN, PMMA, PVAc and PLA; the two-dimensional material comprises graphene, graphene oxide, reduced graphene oxide, graphite alkyne, boron nitride, black phosphorus and MoS 2 One or more of transition metal chalcogenide compounds; the solvent comprises one or more of DMF, DMSO, isopropanol, toluene, chlorobenzene, acetic acid and other solutions;
the voltage adopted by the high-voltage electrostatic jet molding technology is 1-30kV; the aperture of the nozzle is 1-50 μm;
the aging treatment under the low temperature condition is to place the nano composite fiber membrane in a temperature and humidity box with the temperature of 20-70 ℃ and the humidity of 20-80%, then place the nano composite fiber membrane in a blast drying box with the temperature of 200-300 ℃, and finally use plasma or ultraviolet ozone equipment for treatment;
in the preparation method of the photocatalytic fiber membrane, the carbonization and the functionalization treatment under the high-temperature condition adopt an atmosphere furnace sintering mode, and the carbonization and the functionalization treatment are respectively carried out under the atmosphere of air, argon, mixed gas and the like under the temperature condition of 500-900 DEG CMiddle heat preservation is favorable for photocatalysis Carbonizing and functionalizing the chemical fiber.The mixed atmosphere is composed of argon, oxygen and H 2 S and ammonia gas or a plurality of S and ammonia gas.
The following are TiO provided by embodiments of the present invention by way of specific embodiments and comparative examples 2 The preparation and the performance difference of the base/two-dimensional material nano composite photocatalytic fiber membrane are explained in detail.
Example 1
2 parts by weight of graphene was replaced with H 2 Cleaning after S treatment for 30min,Drying, and treating for 15min by using plasma equipment to obtain modified graphene; preparing TiO 2 The matrix/two-dimensional material precursor solution comprises 0.1 part by weight of tetrabutyl titanate, 0.01 part by weight of CdSe quantum dots, 90 parts by weight of PAN, 2 parts by weight of modified graphene, 1000 parts by weight of isopropanol and 500 parts by weight of acetic acid; printing TiO on a printing substrate by adopting a high-voltage electrostatic jet forming technology under the conditions that the voltage is 15kV and the aperture of a nozzle is 10 mu m 2 The preparation method comprises the steps of preparing a base/two-dimensional material nano composite photocatalytic fiber membrane, storing the photocatalytic fiber membrane in a temperature and humidity box with the temperature of 50 ℃ and the humidity of 30% for 24 hours, then storing the photocatalytic fiber membrane in a blast drying box with the temperature of 200 ℃ for 6 hours, and finally treating the photocatalytic fiber membrane for 60 minutes by using plasma equipment; the photocatalytic fiber film is aged and then placed in an atmosphere furnace for sintering, the temperature is respectively kept for 3h, 3h and 5h in three atmospheres of air, argon and oxygen mixed gas under the temperature condition of 800 ℃, the SEM image of the composite fiber is shown in figure 2 (a), and the TEM image is shown in figure 3 (a). As can be seen from the figure, the modified graphene wraps TiO containing CdSe quantum dots 2 And the carbon fiber is distributed in a bead shape.
Comparative example
Preparing to obtain TiO without adding two-dimensional material 2 The base precursor solution, other conditions and operation mode are unchanged, and meanwhile, the conditions and operation of aging treatment and surface modification under low temperature condition, carbonization and functionalization treatment under high temperature condition are the same as those of the embodiment, so that TiO is obtained 2 The nano photocatalytic fiber film is prepared. The SEM image is shown in FIG. 2 (b), and the TEM image is shown in FIG. 3 (b). As can be seen from the figure, tiO 2 The base material is uniformly attached to the surface of the carbon fiber.
The TiO obtained in example 1 2 Base/two-dimensional material nano composite photocatalytic fiber membrane and TiO obtained by comparative example 2 The base nanometer photocatalytic fiber membranes are respectively used for degrading methylene blue light, and the degradation efficiency graph is shown in figure 4. The degradation rate of the example was 98.42%, and the degradation rate of the comparative example was 96.27%. TiO 2 2 The degradation efficiency of the base/two-dimensional material nano composite photocatalytic fiber membrane is obviously superior to that of TiO 2 The degradation efficiency of the nano photocatalytic fiber membrane is improved.
The TiO obtained in example 1 2 Base/two-dimensional material nano composite photocatalytic fiber membrane and TiO obtained by comparative example 2 The base nano photocatalytic fiber membranes were subjected to mechanical property tests, and the test results are shown in fig. 5. The tensile strength of the examples was 237.28cN/dtex, and the tensile strength of the comparative examples was 95.76cN/dtex. TiO 2 2 The mechanical property of the base/two-dimensional material nano composite photocatalytic fiber membrane is obviously superior to that of TiO 2 The mechanical property of the base nanometer photocatalysis fiber membrane.
In TiO 2 On the basis of preparing the base/two-dimensional material nano composite photocatalytic fiber film, the diversified application of the photocatalytic fiber can be realized by further improving the printing modes of printing a substrate, printing patterns and a product structure.
In one implementation, in the preparation method of the photocatalytic fiber membrane, rapid prototyping printing can be directly performed on the surface of a rigid, flexible and curved substrate by using a high-voltage electrostatic jet forming technology, as shown in fig. 6 (a) - (c);
in another implementation manner, in the preparation method of the photocatalytic fiber film, after the substrate surface is covered with the patterned template, the complex pattern can be printed by using the high-voltage electrostatic jet forming technology, as shown in fig. 6 (d);
in another implementation manner, in the preparation method of the photocatalytic fiber film, the surface of the substrate may be printed with the nano composite fiber film, and then printed with other functional materials, so as to obtain a multifunctional junction device, as shown in fig. 6 (e);
as can be seen from the above, the TiO provided by the embodiment of the present invention 2 A base/two-dimensional material nano composite photocatalytic fiber membrane, tiO is wrapped by a two-dimensional material 2 Based on the precursor material, the precursor material is prepared into a bead string-shaped or pea-shaped nano composite fiber structure film by a jet forming technology. The photocatalytic fiber film has the advantages of high photocatalytic activity, good toughness and repeated use, can realize rapid molding on the surface of a rigid, flexible and curved substrate and preparation of complex patterns and multifunctional devices, and can meet the application in the energy environment fields of photodegradation, photocatalytic energy storage, optical detection and the like and the civil field of wearable clothes and the likeAnd (4) demand.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (5)
1. TiO 2 2 The preparation method of the base/two-dimensional material nano composite photocatalytic fiber membrane is characterized by comprising the following steps of:
(1) Carrying out surface modification treatment on the two-dimensional material to obtain the two-dimensional material with the surface rich in functional groups; the surface modification treatment of the two-dimensional material is carried out for 30-150min by using a modification solution, then the two-dimensional material is cleaned and dried, and then the two-dimensional material is treated for 10-120min by using a plasma or ultraviolet ozone device; wherein the modifying solution comprises H 2 S、NH 3 ·H 2 O、KMnO 4 One or more of aqueous solutions;
(2)TiO 2 preparing a base/two-dimensional material precursor solution;
(3) Printing TiO on the surface of a substrate by adopting a high-voltage electrostatic jet forming technology 2 A base/two-dimensional material nano composite photocatalytic fiber membrane;
(4) Aging and surface modifying at low temperature, storing the nanometer composite fiber membrane in a temperature and humidity box with temperature of 20-70 deg.C and humidity of 20-80% for 2-48h, then storing in a forced air drying box with temperature of 200-300 deg.C for 2-8h, and finally treating with plasma or ultraviolet ozone equipment for 10-120min;
(5) Carbonizing and functionalizing under a high-temperature condition, and respectively preserving the heat of the nano composite fiber membrane for 3 hours under the air atmosphere condition of 500 ℃ and preserving the heat of the nano composite fiber membrane for 3 hours and 5 hours under the argon and oxygen mixed gas atmosphere of 800 ℃;
prepared TiO 2 TiO is wrapped by two-dimensional material in the base/two-dimensional material nano composite photocatalytic fiber membrane 2 Preparing a bead string-shaped or pea-shaped nano composite fiber structure film by using a precursor material through a jet forming technology;
the TiO in the step (2) 2 The base/two-dimensional material precursor solution comprisesThe following components:
wherein, the TiO is 2 The base precursor consists of a titanium source and a functional additive material;
the titanium source comprises one or more of titanium isopropoxide, titanium tetrachloride, tetrabutyl titanate and titanium sulfate;
the functional additive material comprises inorganic salt containing B, N, sn and Mn elements, znO nanocrystal and SnO 2 One or more of nanocrystalline, carbon quantum dots and CdSe quantum dots;
the polymer comprises one or more of PVP, PAN, PMMA, PVAc and PLA;
the two-dimensional material comprises graphene, graphene oxide, graphite alkyne, boron nitride, black phosphorus and MoS 2 One or more of the above;
the solvent comprises one or more of DMF, DMSO, isopropanol, toluene, chlorobenzene and acetic acid.
2. The method according to claim 1, wherein the high voltage electrostatic jet forming technique in step (3) uses a voltage of 1-30kV; the aperture of the nozzle is 1-50 μm; the printing substrate is a rigid, flexible or curved substrate.
3. The method of claim 1, wherein in step (3), after the patterned template is covered on the surface of the substrate, the high-voltage electrostatic jet forming technology is used for printing the photocatalytic fiber membrane with complex patterns.
4. The method of claim 1, wherein the step (3) is to print the nanocomposite fiber film on the surface of the substrate and then print other functional materials to obtain the multifunctional junction device.
5. TiO produced by the method according to any one of claims 1 to 4 2 The base/two-dimensional material nano composite photocatalytic fiber membrane is characterized in that the photocatalytic fiber membrane is applied to the fields of photodegradation, photocatalytic energy storage and optical detection energy environment or is used for wearable clothes.
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