CN111215140A - High-molecular composite membrane material with photocatalytic activity and preparation method thereof - Google Patents
High-molecular composite membrane material with photocatalytic activity and preparation method thereof Download PDFInfo
- Publication number
- CN111215140A CN111215140A CN201911250475.5A CN201911250475A CN111215140A CN 111215140 A CN111215140 A CN 111215140A CN 201911250475 A CN201911250475 A CN 201911250475A CN 111215140 A CN111215140 A CN 111215140A
- Authority
- CN
- China
- Prior art keywords
- solution
- polymer composite
- spinning
- zinc oxide
- zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 40
- 239000012528 membrane Substances 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000011787 zinc oxide Substances 0.000 claims abstract description 60
- 238000009987 spinning Methods 0.000 claims abstract description 59
- 229920000642 polymer Polymers 0.000 claims abstract description 47
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 42
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 38
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011701 zinc Substances 0.000 claims abstract description 32
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 32
- 239000002861 polymer material Substances 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 16
- 150000000917 Erbium Chemical class 0.000 claims abstract description 15
- 150000001206 Neodymium Chemical class 0.000 claims abstract description 15
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000005530 etching Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 15
- 229910052693 Europium Inorganic materials 0.000 claims description 12
- 230000007613 environmental effect Effects 0.000 claims description 12
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 12
- 238000011065 in-situ storage Methods 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical group [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims description 7
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 7
- 239000004626 polylactic acid Substances 0.000 claims description 7
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical group [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 abstract description 6
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- 238000001523 electrospinning Methods 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 238000005286 illumination Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/52—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated carboxylic acids or unsaturated esters
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of photocatalysis, in particular to a high-molecular composite membrane material with photocatalytic activity and a preparation method thereof, and the preparation method comprises the following steps: s1: dissolving a polymer material in an N, N-dimethylformamide solution, and stirring to obtain a solution A; dispersing europium nitrate and a zinc source precursor in an acetone solution to obtain a solution B; mixing the prepared solution A and the prepared solution B to obtain a spinning solution; s2: performing electrostatic spinning on the spinning solution obtained in the step S1, and performing high-temperature heat treatment to obtain a nano zinc oxide/high polymer composite film; s3: and (3) etching the nano zinc oxide/polymer composite film prepared by S2 by using plasma, adding an acetone solution of soluble erbium salt or soluble neodymium salt, reacting for 1-2h, and calcining to obtain the nano zinc oxide/polymer composite film. The modified nano zinc oxide and erbium oxide and neodymium oxide generated by the hydrolysis of the surface of the film have synergistic effect, so that the polymer composite film material has excellent photocatalytic activity.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a high-molecular composite membrane material with photocatalytic activity and a preparation method thereof.
Background
With the increasing importance of the country and government on environmental protection, the topic of environmental governance is receiving wide attention. The photocatalytic material is widely applied due to the catalytic degradation of harmful substances in the wastewater to a certain degree, wherein inorganic oxides such as nano zinc oxide, nano titanium dioxide and other nano materials play an important role in the fields of textile, coating, wastewater treatment and the like due to the characteristics of excellent photocatalytic performance, good stability, large specific surface area and the like. However, the response range of the nano zinc oxide and the titanium dioxide to light is in the ultraviolet region, the nano zinc oxide and the titanium dioxide cannot play a photocatalysis role in the visible light range to degrade dirt, and photo-generated electrons and holes generated under the illumination condition are easy to be compounded, so that the two factors limit the application of the nano zinc oxide and the titanium dioxide to a certain extent.
Inorganic oxides such as nano zinc oxide, nano titanium dioxide and the like are modified to enable other elements to enter between crystal lattices, so that the response range of the elements to illumination can be extended to a visible light region, in addition, photo-generated electrons and holes can be effectively separated, and the photocatalytic activity of the elements is improved. The direct application of inorganic oxide or its aqueous dispersion in sewage treatment results in poor recoverability and resource waste, and the inorganic oxide or its aqueous dispersion is generally applied to a film
At present, the traditional photocatalytic composite film usually adopts a direct coating process, on one hand, the photocatalyst is unevenly loaded and is easy to agglomerate, on the other hand, the photocatalyst has poor stability in the film, and the thermal stability of the film is poor, so that the photocatalytic activity of the photocatalytic film is influenced, and therefore, the development of the photocatalytic composite film with good stability and good photocatalytic activity is needed.
Disclosure of Invention
In order to solve the technical problems, the invention aims to endow the antibacterial compound with excellent broad-spectrum antibacterial activity by adding the zinc-doped graphene quantum dots into the antibacterial polymer matrix in an in-situ blending mode and by using the graphene quantum dots, zinc ions, imidazole groups and hydrophobic fluorine-containing monomers in the system, and the antibacterial compound is not easy to migrate and volatilize, long-acting and durable in antibacterial effect, small in toxicity and good in biocompatibility.
In order to achieve the above object, the technical solution of the present invention is as follows.
A preparation method of a high-molecular composite membrane material with photocatalytic activity comprises the following steps:
s1: dissolving a polymer material in an N, N-dimethylformamide solution, and stirring to obtain a solution A; dispersing europium nitrate and a zinc source precursor in an acetone solution to obtain a solution B; mixing the prepared solution A and the prepared solution B in a mass ratio of 1-2: 1 to obtain a spinning solution;
s2: transferring the spinning solution obtained in the step S1 to an electrostatic spinning machine for spinning, wherein a zinc source is hydrolyzed in situ to generate nano zinc oxide, europium element enters zinc nano zinc oxide crystal lattices in a doping mode while being hydrolyzed to uniformly grow on a polymer composite film formed by a polymer material, and the nano zinc oxide/polymer composite film is obtained through heat treatment;
s3: and (3) etching the nano zinc oxide/polymer composite film obtained in the step (S2) by using plasma, adding an acetone solution of soluble erbium salt or soluble neodymium salt, reacting for 1-2h, and calcining to obtain the nano zinc oxide/polymer composite film.
Preferably, the polymer material in S1 is one of polylactic acid, polymethyl methacrylate, polyvinyl alcohol, polyethylene, polystyrene, and polyacrylonitrile.
Preferably, in S1, the zinc source precursor is one of zinc acetate, zinc nitrate, zinc sulfate, and zinc chloride.
Preferably, in S1, the solution a includes the following components in parts by weight: 60-90 parts of polymer material and 30-40 parts of N, N-dimethylformamide; solution B comprises the following components: 1-2 parts of europium nitrate, 6-8 parts of a zinc source precursor and 30-40 parts of acetone.
Preferably, the constant conditions of the electrospinning in S2 are: the spinning temperature is 25-50 ℃, the environmental humidity is less than 45%, and the working parameters of the electrostatic spinning machine are as follows: spinning voltage is 10-20kV, the advancing speed of the spinning solution is 0.02-0.1mL/h, and the receiving distance is 10-15 cm.
Preferably, in S2, the temperature of the heat treatment is 180-200 ℃ and the time is 1-1.5 h.
Preferably, in S3, the soluble erbium salt is erbium nitrate and the soluble neodymium salt is neodymium nitrate; the polymer composite film material also comprises 1-2 parts of soluble erbium salt and 1-2 parts of soluble neodymium salt by weight.
Preferably, in S3, the calcination process is performed as follows:
firstly, calcining at 100-180 ℃ for 3-6 h; then, the temperature is programmed to 260-320 ℃ at a speed of 5-10 ℃/min, and the calcination is carried out for 1-2h at 260-320 ℃.
The invention also provides a polymer composite membrane material with photocatalytic activity, which is prepared according to the preparation method.
The invention has the beneficial effects that:
(1) according to the method, the rare earth element europium is used for carrying out in-situ doping modification on the nano zinc oxide generated by hydrolyzing the zinc source precursor, so that the response range of the nano zinc oxide to illumination can be prolonged to a visible light region, photo-generated electrons and holes can be separated, and the photocatalytic activity of the nano zinc oxide is improved.
(2) The invention prepares the high molecular composite membrane by electrostatic spinning, which is beneficial to improving the stability of the nano zinc oxide in the membrane material.
(3) According to the invention, erbium salt and neodymium salt are hydrolyzed and deposited on the surface of the film through plasma etching treatment, and the film is endowed with excellent photocatalytic activity through the synergistic effect of the modified nano zinc oxide and erbium oxide and neodymium oxide generated by the hydrolysis of the surface of the film.
Detailed Description
The present invention will be described in detail with reference to specific embodiments, but it should be understood that the scope of the present invention is not limited by the specific embodiments. The test methods not specified in the following examples are generally conducted under conventional conditions, and the sources of the test materials not specified are commercially available, and the steps thereof will not be described in detail since they do not relate to the invention.
A preparation method of a high-molecular composite membrane material with photocatalytic activity comprises the following steps:
s1: dissolving a polymer material in an N, N-dimethylformamide solution, and stirring to obtain a solution A; dispersing europium nitrate and a zinc source precursor in an acetone solution to obtain a solution B; mixing the prepared solution A and the prepared solution B according to a proportion to obtain a spinning solution;
s2: transferring the spinning solution obtained in the step S1 to an electrostatic spinning machine for spinning under a constant condition, wherein a zinc source is hydrolyzed in situ to generate nano zinc oxide, europium element enters zinc nano zinc oxide crystal lattices in a doping mode while being hydrolyzed to uniformly grow on a polymer composite film formed by a polymer material, and the nano zinc oxide/polymer composite film is obtained through high-temperature heat treatment;
s3: and (3) etching the nano zinc oxide/polymer composite film obtained in the step (S2) by using plasma, adding an acetone solution of soluble erbium salt or soluble neodymium salt, reacting for 1-2h, and then carrying out low-temperature treatment and high-temperature calcination to obtain the nano zinc oxide/polymer composite film.
Preferably, the polymer material in S1 is one of polylactic acid, polymethyl methacrylate, polyvinyl alcohol, polyethylene, polystyrene, and polyacrylonitrile.
Preferably, in S1, the zinc source precursor is one of zinc acetate, zinc nitrate, zinc sulfate, and zinc chloride.
Preferably, in S1, the solution a includes the following components in parts by weight: 60-90 parts of polymer material and 30-40 parts of N, N-dimethylformamide; solution B comprises the following components: 1-2 parts of europium nitrate, 6-8 parts of a zinc source precursor and 30-40 parts of acetone.
Preferably, the ratio of solution a to solution B in S2 is 1: 1.
Preferably, the constant conditions of the electrospinning in S2 are: the spinning temperature is 25-50 ℃, the environmental humidity is less than 45%, and the working parameters of the electrostatic spinning machine are as follows: spinning voltage is 10-20kV, the advancing speed of the spinning solution is 0.02-0.1mL/h, and the receiving distance is 10-15 cm.
Preferably, the high temperature heat treatment in S2 is 180-200 ℃ for 1-1.5 h.
Preferably, in S3, the soluble erbium salt is erbium nitrate and the soluble neodymium salt is neodymium nitrate; the polymer composite film material also comprises 1-2 parts of soluble erbium salt and 1-2 parts of soluble neodymium salt by weight.
Preferably, in S3, the low-temperature treatment process is performed as follows: calcining at 100-180 ℃ for 3-6 h; the operation process of the high-temperature calcination treatment process is as follows: after the low temperature treatment is finished, the temperature is programmed to 260-320 ℃ at a speed of 5-10 ℃/min, and the calcination is carried out for 1-2h at 260-320 ℃.
Based on the same inventive concept, the invention also provides a polymer composite membrane material with photocatalytic activity, which is prepared by the preparation method.
The following examples are specifically included.
Example 1
A preparation method of a high-molecular composite membrane material with photocatalytic activity comprises the following steps:
s1: dissolving 60g of polylactic acid in 30g N, N-dimethylformamide solution, and stirring to obtain solution A; 1g of europium nitrate and 6g of zinc acetate are dispersed in 30g of acetone solution to obtain solution B; mixing the prepared solution A and the prepared solution B according to the mass ratio of 1:1 to obtain a spinning solution;
s2: the spinning solution obtained in S1 was transferred to an electrospinning machine under constant conditions: the spinning temperature is 25 ℃, the environmental humidity is 30%, and the working parameters of the electrostatic spinning machine are as follows: spinning at a spinning voltage of 10kV, a spinning solution advancing speed of 0.02mL/h and a receiving distance of 10cm, wherein a zinc source is hydrolyzed in situ to generate nano-zinc oxide, europium element enters zinc nano-zinc oxide crystal lattices in a doping mode while being hydrolyzed to uniformly grow on a polymer composite film formed by a polymer material, and the nano-zinc oxide/polymer composite film is obtained by processing at 180 ℃ for 1 h;
s3: and (2) etching the nano zinc oxide/polymer composite membrane obtained in the step (S2) by using plasma, then adding 1g of erbium nitrate or 1g of neodymium nitrate into the acetone solution, reacting for 1-2h, calcining for 3h at 100 ℃, then heating to 260 ℃ by a speed program of 5 ℃/min, and calcining for 1h at 260 ℃ to obtain the nano zinc oxide/polymer composite membrane.
Example 2
A preparation method of a high-molecular composite membrane material with photocatalytic activity comprises the following steps:
s1: dissolving 90g of polymethyl methacrylate in 40g of N, N-dimethylformamide solution, and stirring to obtain a solution A; dispersing 2g of europium nitrate and 8g of zinc nitrate in 40g of acetone solution to obtain solution B; mixing the prepared solution A and the solution B according to the proportion of 1:1 to obtain spinning solution;
s2: the spinning solution obtained in S1 was transferred to an electrospinning machine under constant conditions: the spinning temperature is 50 ℃, the environmental humidity is 40%, and the working parameters of the electrostatic spinning machine are as follows: spinning at a spinning voltage of 20kV and a spinning solution advancing speed of 0.1mL/h and a receiving distance of 15cm, wherein a zinc source is hydrolyzed in situ to generate nano-zinc oxide, europium element enters zinc nano-zinc oxide crystal lattices in a doping mode while being hydrolyzed to uniformly grow on a polymer composite film formed by a polymer material, and the nano-zinc oxide/polymer composite film is obtained by performing high-temperature heat treatment at 200 ℃ for 1.5 h;
s3: and (3) etching the nano zinc oxide/polymer composite membrane obtained in the step (S2) by using plasma, then adding 2g of erbium nitrate or 2g of neodymium nitrate, reacting for 1-2h, calcining for 6h at 180 ℃, then heating to 320 ℃ by a speed program of 10 ℃/min, and calcining for 2h at 320 ℃ to obtain the nano zinc oxide/polymer composite membrane.
Example 3
A preparation method of a high-molecular composite membrane material with photocatalytic activity comprises the following steps:
s1: dissolving 70g of polystyrene in 35g of N, N-dimethylformamide solution, and stirring to obtain a solution A; 1.5g of europium nitrate and 7g of zinc chloride are dispersed in 35g of acetone solution to obtain solution B; mixing the prepared solution A and the solution B according to the proportion of 1:1 to obtain spinning solution;
s2: the spinning solution obtained in S1 was transferred to an electrospinning machine under constant conditions: the spinning temperature is 35 ℃, the environmental humidity is 30%, and the working parameters of the electrostatic spinning machine are as follows: spinning at a spinning voltage of 15kV, a spinning solution advancing speed of 0.05mL/h and a receiving distance of 12cm, wherein a zinc source is hydrolyzed in situ to generate nano-zinc oxide, europium element enters zinc nano-zinc oxide crystal lattices in a doping mode while being hydrolyzed to uniformly grow on a polymer composite film formed by a polymer material, and the nano-zinc oxide/polymer composite film is obtained by high-temperature heat treatment at 190 ℃ for 1.2 h;
s3: and (2) etching the nano zinc oxide/polymer composite membrane obtained in the step (S2) by using plasma, then adding 1.5g of erbium nitrate or 1.5g of neodymium nitrate into the acetone solution, reacting for 1-2h, calcining for 4h at 150 ℃, then heating to 280 ℃ by a program at a speed of 8 ℃/min, and calcining for 1.5h at 280 ℃ to obtain the nano zinc oxide/polymer composite membrane.
Comparative example 1
A preparation method of a high-molecular composite membrane material with photocatalytic activity comprises the following steps:
s1: dissolving 60g of polylactic acid in 30g of N, N-dimethylformamide solution, and stirring to obtain solution A; 1g of europium nitrate and 6g of zinc acetate are dispersed in 30g of acetone solution to obtain solution B; mixing the prepared solution A and the solution B according to the proportion of 1:1 to obtain spinning solution;
s2: the spinning solution obtained in S1 was transferred to an electrospinning machine under constant conditions: the spinning temperature is 25 ℃, the environmental humidity is 40%, and the working parameters of the electrostatic spinning machine are as follows: spinning at 10kV, the advancing speed of the spinning solution is 0.02mL/h, the receiving distance is 10cm, a zinc source is hydrolyzed in situ to generate nano-zinc oxide, europium element enters zinc nano-zinc oxide crystal lattices in a doping mode while being hydrolyzed to uniformly grow on a polymer composite film formed by a polymer material, and the nano-zinc oxide/polymer composite film is obtained by high-temperature heat treatment at 180 ℃ for 1 h.
Comparative example 2
A preparation method of a high-molecular composite membrane material with photocatalytic activity comprises the following steps:
s1: dissolving 90g of polymethyl methacrylate polymer material in 40g of N, N-dimethylformamide solution, and stirring to obtain a solution A; dispersing 8g of zinc nitrate in 40g of acetone solution to obtain a solution B; mixing the prepared solution A and the solution B according to the proportion of 1:1 to obtain spinning solution;
s2: the spinning solution obtained in S1 was transferred to an electrospinning machine under constant conditions: the spinning temperature is 50 ℃, the environmental humidity is 35%, and the working parameters of the electrostatic spinning machine are as follows: spinning at a spinning voltage of 20kV, a spinning solution advancing speed of 0.1mL/h and a receiving distance of 15cm, wherein a zinc source is hydrolyzed in situ to generate nano-zinc oxide, europium element enters zinc nano-zinc oxide crystal lattices in a doping mode while being hydrolyzed to uniformly grow on a polymer composite film formed by a polymer material, and the nano-zinc oxide/polymer composite film is obtained by high-temperature heat treatment at 200 ℃ for 1.5 h;
s3: and (3) etching the nano zinc oxide/polymer composite membrane obtained in the step (S2) by using plasma, then adding 2g of erbium nitrate or 2g of neodymium nitrate acetone solution, reacting for 1-2h, calcining for 6h at 180 ℃, and then heating to 320 ℃ by a program and calcining for 2h to obtain the nano zinc oxide/polymer composite membrane.
Comparative example 3
A preparation method of a high-molecular composite membrane material with photocatalytic activity comprises the following steps:
s1: dissolving 90g of polylactic acid in 40g of N, N-dimethylformamide solution, and stirring to obtain a solution A; dispersing 8g of zinc chloride in 40g of acetone solution to obtain solution B; mixing the prepared solution A and the solution B according to the proportion of 1:1 to obtain spinning solution;
s2: the spinning solution obtained in S1 was transferred to an electrospinning machine under constant conditions: the spinning temperature is 35 ℃, the environmental humidity is 25%, and the working parameters of the electrostatic spinning machine are as follows: spinning at 15kV, the advancing speed of the spinning solution is 0.05mL/h, the receiving distance is 12cm, a zinc source is hydrolyzed in situ to generate nano-zinc oxide, europium element enters zinc nano-zinc oxide crystal lattices in a doping mode while being hydrolyzed to uniformly grow on a polymer composite film formed by a polymer material, and the nano-zinc oxide/polymer composite film is obtained by high-temperature heat treatment at 190 ℃ for 1.2 h.
Comparative example 4
A preparation method of a high-molecular composite membrane material with photocatalytic activity comprises the following steps:
s1: dissolving 90g of polylactic acid in 40g of N, N-dimethylformamide solution, and stirring to obtain a spinning solution;
s2: the spinning solution obtained in S1 was transferred to an electrospinning machine under constant conditions: the spinning temperature is 35 ℃, the environmental humidity is 25%, and the working parameters of the electrostatic spinning machine are as follows: spinning at 15kV, the advancing speed of the spinning solution of 0.05mL/h and the receiving distance of 12cm, and carrying out high-temperature heat treatment at 190 ℃ for 1.2h to obtain the nano zinc oxide/polymer composite membrane.
Evaluation of photocatalytic degradation Properties
The samples prepared in the above examples 1 to 3 and comparative examples 1 to 4 were subjected to photocatalytic degradation performance evaluation tests by the following methods:
preparing 5mg/L rhodamine B solution, adding 50mg of the prepared sample into the solution, adsorbing for 30min under dark condition, irradiating for 60min under 400W ultraviolet lamp, and testing absorbance of supernatant liquid at 553nm by using an ultraviolet spectrophotometer.
The degradation rate of the dye was calculated by the following formula:
r% (degradation rate) ═ C0-Ct)/C0*100%
In the above formula: c0Is the initial concentration of rhodamine B dye, CtRefers to the concentration of rhodamine B dye at a particular time.
The test results are shown in table 1.
TABLE 1 dye degradation rate test results (%)
Inspection item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
Rate of dye degradation | 98.6 | 99.3 | 98.9 | 89.1 | 83.6 | 73.2 | 10.7 |
From the above results, it can be seen that in examples 1 to 3, since the rare earth element europium modifies the nano zinc oxide formed by hydrolysis of the zinc source precursor to improve its photocatalytic activity, and further erbium salt and neodymium salt are hydrolyzed and deposited on the surface of the film by plasma treatment, the modified nano zinc oxide and erbium oxide and neodymium oxide formed by hydrolysis of the surface of the film act synergistically to impart excellent photocatalytic activity to the film, and therefore the degradation efficiency for rhodamine B dye can be up to 98% or more.
Compared with the examples 1-3, the plasma etching deposition is carried out without adding soluble erbium salt and soluble neodymium salt in the comparative example 1, the photocatalytic activity is lower than that of the examples 1-3, and the degradation efficiency is 89.1%;
in comparative example 2, europium nitrate is not added, and the europium nitrate and the zinc source precursor are hydrolyzed simultaneously in S1 to modify the generated nano zinc oxide, so that the photocatalytic activity of the nano zinc oxide is lower than that of examples 1-3, and the degradation efficiency is 83.6%;
comparative example 3 no europium source was added in S1 and no soluble erbium salt and soluble neodymium salt were plasma etch deposited in S3, thus the photocatalytic activity was lower than that of examples 1-3, and the degradation efficiency was 73.2%;
comparative example 4 was a composite film obtained by electrospinning only a polymer material without adding a zinc source, europium nitrate, a soluble erbium salt and a soluble neodymium salt, and thus, its photocatalytic activity was lower than that of examples 1 to 3, its degradation efficiency was 10.7%, and it had substantially no photocatalytic degradation activity.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A preparation method of a high-molecular composite membrane material with photocatalytic activity is characterized by comprising the following steps:
s1: dissolving a polymer material in an N, N-dimethylformamide solution, and stirring to obtain a solution A; dispersing europium nitrate and a zinc source precursor in an acetone solution to obtain a solution B; mixing the prepared solution A and the prepared solution B in a mass ratio of 1-2: 1 to obtain a spinning solution;
s2: transferring the spinning solution obtained in the step S1 to an electrostatic spinning machine for spinning, wherein a zinc source is hydrolyzed in situ to generate nano zinc oxide, europium element enters zinc nano zinc oxide crystal lattices in a doping mode while being hydrolyzed to uniformly grow on a polymer composite film formed by a polymer material, and the nano zinc oxide/polymer composite film is obtained through heat treatment;
s3: and (3) etching the nano zinc oxide/polymer composite film obtained in the step (S2) by using plasma, adding an acetone solution of soluble erbium salt or soluble neodymium salt, reacting for 1-2h, and calcining to obtain the nano zinc oxide/polymer composite film.
2. The method for preparing a polymer composite membrane material with photocatalytic activity according to claim 1, wherein the polymer material in S1 is one of polylactic acid, polymethyl methacrylate, polyvinyl alcohol, polyethylene, polystyrene, and polyacrylonitrile.
3. The method of claim 1, wherein in S1, the zinc source precursor is one of zinc acetate, zinc nitrate, zinc sulfate, and zinc chloride.
4. The method for preparing a polymer composite membrane material with photocatalytic activity according to claim 1, wherein in S1, the solution a comprises the following components in parts by weight: 60-90 parts of polymer material and 30-40 parts of N, N-dimethylformamide; solution B comprises the following components: 1-2 parts of europium nitrate, 6-8 parts of a zinc source precursor and 30-40 parts of acetone.
5. The method for preparing a polymer composite membrane material with photocatalytic activity according to claim 1, wherein the electrostatic spinning conditions in S2 are as follows: the spinning temperature is 25-50 ℃, the environmental humidity is less than 45%, and the working parameters of the electrostatic spinning machine are as follows: spinning voltage is 10-20kV, the advancing speed of the spinning solution is 0.02-0.1mL/h, and the receiving distance is 10-15 cm.
6. The method as claimed in claim 1, wherein the heat treatment temperature in S2 is 180-200 ℃ and the time is 1-1.5 h.
7. The method according to claim 1, wherein in S3, the soluble erbium salt is erbium nitrate and the soluble neodymium salt is neodymium nitrate.
8. The method according to claim 7, wherein the polymer composite film material further comprises 1-2 parts by weight of soluble erbium salt and 1-2 parts by weight of soluble neodymium salt.
9. The method according to claim 1, wherein the calcination process in S3 is performed as follows:
firstly, calcining at 100-180 ℃ for 3-6 h; then, the temperature is programmed to 260-320 ℃ at a speed of 5-10 ℃/min, and the calcination is carried out for 1-2h at 260-320 ℃.
10. A polymer composite membrane material with photocatalytic activity prepared by the preparation method according to any one of claims 1 to 9.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911250475.5A CN111215140A (en) | 2019-12-09 | 2019-12-09 | High-molecular composite membrane material with photocatalytic activity and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911250475.5A CN111215140A (en) | 2019-12-09 | 2019-12-09 | High-molecular composite membrane material with photocatalytic activity and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111215140A true CN111215140A (en) | 2020-06-02 |
Family
ID=70830749
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201911250475.5A Pending CN111215140A (en) | 2019-12-09 | 2019-12-09 | High-molecular composite membrane material with photocatalytic activity and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111215140A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113351233A (en) * | 2021-04-09 | 2021-09-07 | 南通大学 | Tetracycline purification fiber membrane and preparation method thereof |
CN115106077A (en) * | 2022-06-24 | 2022-09-27 | 西南科技大学 | Preparation and application of erbium-doped zinc oxide nanosheet based on photocatalytic reduction of uranium |
CN116333642A (en) * | 2022-12-30 | 2023-06-27 | 上海朗亿功能材料有限公司 | Composite EVA material, adhesive film, preparation method and application of adhesive film, and battery assembly |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1772375A (en) * | 2005-10-27 | 2006-05-17 | 南京大学 | Nanometer doped zinc oxide and its prepn and application in photocatalysis to degrade organic matter and kill bacteria |
CN108855236A (en) * | 2018-07-17 | 2018-11-23 | 成都市水泷头化工科技有限公司 | A kind of recyclable high temperature resistant photocatalysis film and preparation method for sewage treatment |
-
2019
- 2019-12-09 CN CN201911250475.5A patent/CN111215140A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1772375A (en) * | 2005-10-27 | 2006-05-17 | 南京大学 | Nanometer doped zinc oxide and its prepn and application in photocatalysis to degrade organic matter and kill bacteria |
CN108855236A (en) * | 2018-07-17 | 2018-11-23 | 成都市水泷头化工科技有限公司 | A kind of recyclable high temperature resistant photocatalysis film and preparation method for sewage treatment |
Non-Patent Citations (3)
Title |
---|
董永春: "《纺织助剂化学》", 31 January 2010 * |
陈昕海等: "Nd-Er/ZnO-TiO_2光催化剂对2,4-DCP的光催化降解研究", 《现代化工》 * |
马正先等: "《纳米氧化锌制备原理与技术》", 30 June 2009 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113351233A (en) * | 2021-04-09 | 2021-09-07 | 南通大学 | Tetracycline purification fiber membrane and preparation method thereof |
CN115106077A (en) * | 2022-06-24 | 2022-09-27 | 西南科技大学 | Preparation and application of erbium-doped zinc oxide nanosheet based on photocatalytic reduction of uranium |
CN116333642A (en) * | 2022-12-30 | 2023-06-27 | 上海朗亿功能材料有限公司 | Composite EVA material, adhesive film, preparation method and application of adhesive film, and battery assembly |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111215140A (en) | High-molecular composite membrane material with photocatalytic activity and preparation method thereof | |
CN106223009B (en) | A kind of visible light catalyst self-cleaning antibacterial fabric and its preparation and application | |
CN107201124B (en) | Water-based acrylic coating for purifying air by utilizing negative ions | |
CN107983320B (en) | Preparation method of bifunctional film for removing formaldehyde, product and application thereof | |
CN113289647B (en) | Biochar doped BiOBr x Cl 1-x Photocatalyst, preparation method and application | |
CN104437466B (en) | A kind of CNT is combined the preparation method of pucherite green deep water treatment agent | |
CN104525173B (en) | A kind of CNT composite Ti O2the preparation method of green deep water treatment agent | |
CN109179796A (en) | Absorption/flocculation/photocatalysis composite dye waste water treating agent and wastewater treatment method | |
CN103920517A (en) | Composite visible light photocatalyst and its preparation method | |
CN110777541A (en) | Anti-aging and antibacterial raincoat fabric | |
US20220331746A1 (en) | Light-driven filtration antibacterial composite membrane and preparation method and use thereof | |
CN103933957B (en) | Porous monocrystalline nano titanium dioxide photocatalyst that a kind of high crystallization, size are controlled, high-energy surface exposes and its preparation method and application | |
CN105964248A (en) | Preparation method of coal ash microsphere loaded modified nanometer titanium dioxide composite photocatalyst | |
CN108144583A (en) | It is a kind of novel except the preparation method of formaldehyde activity charcoal | |
CN108893976B (en) | Method for improving attachment amount and uniformity of silver particles on cotton fabric in reduction process | |
CN104475100B (en) | A kind of CNT is combined the preparation method of bismuth molybdate green deep water treatment agent | |
CN113788900A (en) | Modified cellulose nanocrystal with high thermal stability and preparation method thereof | |
CN102517887A (en) | Method for preparing silicon protective in-situ deposition photocatalytic functional textile | |
CN109319877B (en) | Method for treating organic wastewater by using zirconia/titanium dioxide composite nanofiber material | |
CN104528865B (en) | A kind of CNT composite S rFeO3the preparation method of green deep water treatment agent | |
CN108755103B (en) | Preparation method of photocatalytic self-cleaning anti-ultraviolet fabric | |
CN108179547B (en) | Preparation method of fluorescent nanofiber membrane used as heavy metal antimony visual detector | |
CN114146732A (en) | Polyaniline modified TiO2Composite nanofiber membrane and preparation method and application thereof | |
CN114164511A (en) | Preparation method of porous titanium dioxide mixed polyacrylonitrile fiber | |
CN104525115B (en) | A kind of CNT is combined WO3the preparation method of green deep water treatment agent |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200602 |
|
RJ01 | Rejection of invention patent application after publication |