CN115467158B - Preparation method of photocatalytic formaldehyde-removing antibacterial functional fabric - Google Patents
Preparation method of photocatalytic formaldehyde-removing antibacterial functional fabric Download PDFInfo
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- CN115467158B CN115467158B CN202211212063.4A CN202211212063A CN115467158B CN 115467158 B CN115467158 B CN 115467158B CN 202211212063 A CN202211212063 A CN 202211212063A CN 115467158 B CN115467158 B CN 115467158B
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- 239000004744 fabric Substances 0.000 title claims abstract description 121
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 44
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229920000728 polyester Polymers 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
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- 101710134784 Agnoprotein Proteins 0.000 claims description 11
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- 238000002791 soaking Methods 0.000 claims description 3
- 238000007740 vapor deposition Methods 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 68
- 239000000463 material Substances 0.000 abstract description 23
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- 230000015556 catabolic process Effects 0.000 description 7
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- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
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- 230000004630 mental health Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000009340 pathogen transmission Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/49—Oxides or hydroxides of elements of Groups 8, 9,10 or 18 of the Periodic Table; Ferrates; Cobaltates; Nickelates; Ruthenates; Osmates; Rhodates; Iridates; Palladates; Platinates
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/13—Ammonium halides or halides of elements of Groups 1 or 11 of the Periodic Table
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
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- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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- 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
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a photocatalysis formaldehyde-removing antibacterial functional fabric, which relates to the field of purifying materials, and aims to solve the problems that a traditional fabric uses a short plate, the photocatalysis material is loaded on the fabric to enable the fabric to have formaldehyde-removing performance and antibacterial performance, and in addition, a photocatalyst synthesized by surface plasma effect is low in photocatalysis performance of a single catalyst. In the scheme of the invention, a large amount of Fe is used 2 O 3 While Fe 2 O 3 The natural environment has abundant reserves and wide distribution, is easy to obtain and process, and has no harm to human bodies. The formaldehyde pollution problem is effectively solved, the limitation of the use of the traditional fabric is broken, and the method has remarkable economic benefit.
Description
Technical Field
The invention belongs to the field of formaldehyde purification materials in air and preparation thereof, and particularly relates to a preparation method of a photocatalytic formaldehyde-removing antibacterial functional fabric.
Background
With the rapid development of economy and the improvement of living standard of people, the functional demands of people on outdoor textile fabrics are gradually improved, and the development of the comfort of individuals is focused on the emerging functions and performance directions of ultraviolet resistance, water resistance, oil resistance, self-cleaning, flame retardance, antibiosis and the like, so that the rapid increase of the production demands of textile industry on multifunctional textiles is also caused, and the multifunctionalization of textiles is becoming the focus of research of researchers in various countries. With the development of nanomaterials and nanotechnology, nanomaterials and nanotechnology are increasingly applied to the modification of polyester fabrics in the textile industry due to their attractive and diversified properties. Compared with the traditional textile printing and dyeing process, the nano material load can not only enhance the intrinsic characteristics of the polyester fabric, but also endow the polyester fabric with special self-cleaning performance and antibacterial performance.
In outdoor environments, the existence of bacterial contamination causes a fairly wide range of disease problems, threatening the physical and mental health of the human body. The multifunctional fabric is used in natural environment, and can prevent pathogen transmission and inhibit the growth of harmful microbes, so as to protect human body and ecological environment. The fabric doped with the nano material for surface modification can kill harmful microorganisms through a photocatalysis mechanism under the irradiation of sunlight so as to meet the high requirements of people on the multifunctional fabric. With the advent and maturity of nanomaterial application, a number of nanomaterial-based antimicrobial substances have been developed, including silver, copper, and some other metal or metal-based components, with silver-based antimicrobial substances being the most widely explored materials. Metal oxide nanoparticles, such as copper, zinc and titanium oxides, have been found to have good inhibition of microorganisms in different environments. While the above-described nanomaterials have application in antimicrobial applications, these nanomaterials can cause soil heavy metal contamination or damage to other organisms when released into the environment. In the metal oxide, fe 2 O 3 Nanomaterials have been approved by the U.S. Food and Drug Administration (FDA) for food and medical applications, visible Fe 2 O 3 The nanomaterial has a mild effect on the environment. Because of the advantages of strong magnetism, low toxicity, abundant reserves, low acquisition cost and the like, the Fe-based alloy has more and more attractive effect on expert scholars in the fields of photocatalysis and biomedical research 2 O 3 The electron hole pairs in (a) are not easily separated due to the short hole diffusion length (2-4 nm).
Therefore, it is important to develop a functional fabric which can remove formaldehyde and has antibacterial performance.
Disclosure of Invention
The invention aims to solve the technical problems of providing a photocatalysis formaldehyde-removing antibacterial functional fabric and a preparation method thereof, which complement the traditional fabric to use a short plate, and the photocatalysis material is used for loading the fabric to ensure that the fabric has formaldehyde-removing performance and antibacterial performance, and in addition, the photocatalyst synthesized by the surface plasma effect solves the problem of low photocatalysis performance of a single catalyst.
The invention relates to a preparation method of a photocatalytic formaldehyde-removing antibacterial functional fabric, which comprises the following steps:
step one, fe 2 O 3 Preparation of functional fabrics
Modifying the polyester fabric by adopting NaOH solution under the water bath condition, then washing and drying the polyester fabric by deionized water, and adding the modified fabric into the polyester fabric containing Fe 2 O 3 The powder is stirred magnetically after being evenly dispersed by ultrasonic in deionized water, transferred into a polytetrafluoroethylene high-pressure reaction kettle, subjected to hydrothermal reaction, cooled to room temperature, and dried to prepare Fe 2 O 3 A functional fabric;
the volume mass ratio of the NaOH solution to the polyester fabric is (25-35) mL:1g; fe (Fe) 2 O 3 The concentration of the powder in deionized water is 5-15 mg/L,
step two, ag/AgBr/Fe 2 O 3 Preparation of functional fabrics
Fe prepared in step one by photochemical vapor deposition 2 O 3 Depositing Ag/AgBr on the surface of the functional fabric to prepare Ag/AgBr/Fe 2 O 3 A functional fabric; the photocatalytic formaldehyde-removing antibacterial functional fabric is completed.
After the fabric is pretreated by NaOH alkali liquor, grooves are reserved on the surface of the fabric fiber, which is beneficial to the adhesion of photocatalytic materials.
To prepare Ag/AgBr/Fe 2 O 3 The functional fabric has good antibacterial activity on gram negative bacteria, namely escherichia coli.
To prepare Ag/AgBr/Fe 2 O 3 The functional fabric has high degradation efficiency on volatile organic pollutant formaldehyde.
To prepare Ag/AgBr/Fe 2 O 3 The functional fabric can effectively recycle the photocatalytic material.
Further, the light described in step twoFe prepared in step one by chemical deposition method 2 O 3 The specific operation of depositing Ag/AgBr on the surface of the functional fabric is as follows:
fe is added to 2 O 3 Soaking functional fabric in AgNO 3 Adding KBr powder into the solution to perform light-proof reaction, then placing the solution under a xenon lamp for irradiation, washing the fabric with deionized water after the reaction is finished, and drying to prepare Ag/AgBr/Fe 2 O 3 A functional fabric; wherein AgNO 3 The concentration is 50-250 mg/L;
said Fe 2 O 3 The mass ratio of the functional fabric to KBr powder is 1:0.05 to 0.15;
said Fe 2 O 3 Functional fabric and AgNO 3 The mass ratio of the solution is 1: 20-40.
Further, the drying conditions are as follows: and (3) drying in a 60 ℃ oven for 12 hours, and carrying out light-shielding grinding for 1 hour for later use.
Further, the AgNO 3 The concentration is 50mg/L, 100mg/L, 150mg/L, 200mg/L or 250mg/L.
Further, the water bath condition in the first step is that the modification is carried out for 40-60 min at the temperature of 60-80 ℃.
Further, the time for uniformly dispersing the ultrasonic waves in the first step is 20-40 min.
Further, the hydrothermal reaction condition in the first step is that the hydrothermal reaction is carried out for 2-4 hours at the temperature of 80-100 ℃.
Further, the drying condition in the first step is that the drying is carried out in an oven at 60 ℃ for 12 hours.
Further, fe in the first step 2 O 3 The concentration of the powder in deionized water is 10-15 mg/L.
Further, in the first step, the volume mass ratio of the NaOH solution to the polyester fabric is (25-35) mL:1g.
The invention has the following beneficial effects:
(1) The invention adopts the surface plasma modification technology, has simple preparation process, high stability and easy industrialization, and the heterojunction coupling construction composite material can promote charge separationGreatly promote Fe 2 O 3 The photocatalytic performance of the photocatalytic material can realize the full utilization of solar energy, and has high degradation efficiency on formaldehyde gas;
the Ag/AgBr/Fe of the invention 2 O 3 The preparation process of the functional fabric belongs to the surface plasma modification technology, and because the metal Ag has good photogenerated carrier mobility and Fe 2 O 3 The Ag and silver bromide have matched energy band structures, so that higher removal efficiency can be obtained, and high-efficiency separation of photoinduced carriers is realized. Silver halide, especially silver bromide, is an important photosensitive material, and has been widely used in composite photocatalytic systems due to its excellent electronic and photocatalytic properties. Silver bromide is unstable under the illumination condition and is easy to reduce into metal Ag. Therefore, in order to fully utilize the photocatalytic activity, a material is generally modified on silver bromide to inhibit its reduction, thereby improving the stability of silver bromide. Silver bromide and Fe 2 O 3 The constructed heterojunction (the heterojunction) can improve the utilization rate of sunlight, the charge separation efficiency, the oxidation-reduction capability and the carbon dioxide adsorption capability, so that the degradation efficiency of formaldehyde gas is improved, and finally the formaldehyde gas is mineralized into carbon dioxide and water.
(2) AgNO is used in the scheme of the invention 3 The chemical medicine ensures that the silver ions in the functional fabric have antibacterial effect when the functional fabric is used in an outdoor environment, and can effectively prevent harmful bacteria and microorganisms from invading human bodies;
(3) In the scheme of the invention, a large amount of Fe is used 2 O 3 While Fe 2 O 3 The natural environment has abundant reserves and wide distribution, is easy to obtain and process, and has no harm to human bodies. The formaldehyde pollution problem is effectively solved, the limitation of the use of the traditional fabric is broken, and the method has remarkable economic benefit.
The photocatalytic material is loaded on the surface of the functional fabric, and if the functional fabric is used for filtering waste water and degrading flowing water, the photocatalytic material can be recovered, and the functional fabric can be prepared into a multifunctional fabric film, so that the novel photocatalytic material can be used for innovation of the development industry.
Drawings
FIG. 1 is an XRD pattern of different photocatalytic materials in example 2 and example 3;
FIG. 2 is a diagram of Ag/AgBr/Fe in example 3 2 O 3 A performance diagram of photocatalytic formaldehyde removal of the functional fabric;
FIG. 3 is a graph showing the bacteriostatic activity of the different functional fabrics of example 4;
FIG. 4 is a graph of antimicrobial efficiency for various functional fabrics in example 4;
FIG. 5 is an electrochemical EIS diagram of the different photocatalytic materials in example 2 and example 3.
Detailed Description
For the purposes of clarity, technical solutions and advantages of embodiments of the present invention, the spirit of the present disclosure will be described in detail below, and any person skilled in the art, after having appreciated the embodiments of the present disclosure, may make changes and modifications to the techniques taught by the present disclosure without departing from the spirit and scope of the present disclosure.
The exemplary embodiments of the present invention and the descriptions thereof are intended to illustrate the present invention, but not to limit the present invention.
Example 1
The photocatalytic formaldehyde-removing antibacterial functional Ag/AgBr/Fe 2 O 3 The preparation method of the functional fabric comprises the following steps:
step one, fe 2 O 3 Preparation of functional fabrics
Modifying 2×2cm polyester fabric with 30g/L NaOH solution at 70deg.C in water bath for 50min, washing with deionized water, oven drying to remove impurities on the fabric surface, adding modified fabric into a water bath containing commercial Fe 2 O 3 Preparing Fe with concentration of 10mg/L in deionized water of powder 2 O 3 The solution is stirred magnetically for 20min after being evenly dispersed for 30min by ultrasound, transferred into a polytetrafluoroethylene high-pressure reaction kettle, subjected to low-temperature hydrothermal reaction for 3h at 90 ℃, cooled to room temperature and then put into a 60 ℃ oven for dryingDrying for 12h to obtain Fe 2 O 3 A functional fabric;
step two, ag/AgBr/Fe 2 O 3 Preparation of functional fabrics
Fe prepared in step one by photochemical deposition 2 O 3 Depositing Ag/AgBr on the surface of the functional fabric: fe is added to 2 O 3 Soaking functional fabric in AgNO 3 Adding 0.1g KBr powder into the solution for light-shielding reaction for 1h after 30min, placing the solution under a xenon lamp for irradiation for 30min to enable the surface of the solution to be resolved into silver nano particles, washing the fabric with deionized water after the reaction is finished, and drying the fabric in a 60 ℃ oven for 12h for standby to prepare Ag/AgBr/Fe 2 O 3 Functional fabric, agNO 3 The concentration is respectively 50mg/L, 100mg/L, 150mg/L, 200mg/L and 250mg/L. Ag/AgBr/Fe 2 O 3 The photocatalytic material was prepared by the same method, and was dried in an oven at 60℃for 12 hours and then ground in a dark place for 1 hour.
For Fe referred to in example 1 2 O 3 、Ag/AgBr、Ag/AgBr/Fe 2 O 3 Three photocatalytic materials were subjected to X-ray diffraction (XRD) analysis, as shown in fig. 1. At Fe 2 O 3 In the mode, diffraction peaks appear at 24.2 °,33.2 °,35.6 °,40.9 °,43.3 °,49.5 °,54.1 °,57.6 °,62.5 °, and 64.1 °, respectively, corresponding to hematite Fe 2 O 3 (012), (104), (110), (113), (202), (024), (116), (018), (214) (300) crystal planes (JCPLDS No. 33-0664). For the Ag/AgBr mode, diffraction peaks appear at 26.7 °,31.0 °,44.3 °,52.5 °,55.0 °, and 64.5 °, respectively, corresponding to the cubic AgBr (1 1 1), (2 0), (2 2 0), (3 1 1) and (2 2) crystal planes (JCPDS No. 06-0438), respectively. In addition, diffraction peaks of silver nanoparticles were not shown at 38.1 ° in the figure, since the amount of silver nanoparticles was small. In Ag/AgBr/Fe 2 O 3 Fe can still be observed in the composite material 2 O 3 And a strong peak of both Ag/AgBr species.
Example 2
Determination of Formaldehyde removal Property
The photocatalytic formaldehyde removal reaction was carried out in a homemade 7.5L cylindrical quartz reactor. In this processThree pieces of 2X 2cm 2 Is Ag/AgBr/Fe 2 O 3 The functional fabric was placed in a petri dish and placed in a reactor, and then 50 μl of formaldehyde solution was added dropwise as formaldehyde gas volatilization source. Vacuum silicone grease is adopted to seal the bottle mouth of the reactor, when the reactor volatilizes for 1h under a natural state to reach an equilibrium state, a 365nm ultraviolet lamp is used as a light source, and the concentration of formaldehyde is detected by a commercial sensor. Reading balance value C after formaldehyde gas volatilizes for 1h in natural state 0 After the photocatalytic reaction is started by increasing the illumination, the numerical value C is read every ten minutes t The concentration of formaldehyde gas at different times in the quartz reactor was recorded in real time.
A-Formaldehyde removal efficiency
C 0 Initial concentration of formaldehyde at equilibrium in quartz reactor
C t Instantaneous concentration of formaldehyde in quartz reactor at time t
FIG. 2 shows the synthesis of Ag/AgBr/Fe at different silver nitrate concentrations 2 O 3 The degradation efficiency of the functional fabric to formaldehyde gas is increased along with the concentration of silver nitrate, and the prepared Ag/AgBr/Fe 2 O 3 The degradation efficiency of the functional fabric on formaldehyde gas gradually increases, which shows that the photocatalytic activity increases with the addition of silver nitrate (AgNPs), and when the concentration of silver nitrate reaches 250mg/L, the degradation efficiency decreases to 39%. Analysis shows that the agglomeration phenomenon on the surface of the photocatalytic material can be caused by introducing excessive silver nano particles, and the silver nano particles are used for Fe 2 O 3 The material has surface covering and shielding effect, so as to reduce the degradation capability of formaldehyde. Under the excitation of illumination conditions, the electron-hole pair recombination rate of the composite catalyst is reduced, so that the electron transfer capability is improved, and the service life of a carrier is prolonged, which shows that the AgNPs can effectively improve the photoinduction electron transfer efficiency and minimize the electron-hole recombination. Another possible reason is the plasma effect due to the strong interaction between the LSPR band of AgNPs and the incident lightAs can be seen from the figure, at 200mg/L silver nanoparticles in Fe 2 O 3 The loading on the reactor is optimal.
Example 3
Antibacterial property measurement
Coli (gram negative ATCC 25992) is taken as a representative of bacteria, outdoor microbial flora is simulated, and antibacterial performance evaluation is carried out on the finished photocatalytic material-loaded functional fabric through a bacteriostasis circle method and an antibacterial method. And evaluating the antibacterial activity of the functional fabric by adopting a bacteriostasis circle method. Raw fabric, fe 2 O 3 Functional fabric, ag/AgBr/Fe 2 O 3 The functional fabric is cut into a circular sheet with the diameter of 190mm, the circular sheet is lightly attached to the surface of a nutrient agar culture medium inoculated with bacteria and fungi, the inoculation bacterial liquid amount is 100 mu L, then the bacterial culture medium is placed at 37 ℃ for culture for 18 hours, and the size of a transparent bacteriostasis zone on the surface of the bacterial culture medium is observed after the culture is finished so as to judge the bacteriostasis activity of different functional fabrics.
The antibacterial properties of the functional fabrics were evaluated by colony counting. Raw fabric, fe 2 O 3 Functional fabric, ag/AgBr/Fe 2 O 3 Immersing functional fabric in centrifuge tube containing 100 μl of bacterial liquid and 900 μl of solution, shaking, applying 365nm ultraviolet light for 60min, and diluting with PBS solution for 10 min 7 The bacteria liquid of 100 mu L is absorbed and inoculated by a coater, the experimental operation is carried out beside the flame of an alcohol lamp, then the bacteria culture medium is placed at 37 ℃ for culturing for 18 hours, the fungus culture medium is placed at 37 ℃ for culturing for 30 hours, the colony number is recorded, and the average value is obtained by repeating three times. The antibacterial rate is calculated by the following formula:
antibacterial ratio = (A-A) 0 )/A*100％
Wherein: a is the colony number of blank control samples, A 0 Colony count for the experimental samples.
FIG. 3 shows the bacteriostatic activity of different functional fabrics against E.coli, from which it can be seen that the raw fabric and Fe are 2 O 3 The surface of the escherichia coli nutrient agar culture medium of the functional fabric does not observe the transparent inhibition zone around the original fabric, but Ag/AgBr/Fe 2 O 3 Clear visible transparent inhibition zones appear around the functional fabric, and the radius of the inhibition zones is over 2mm after measurement, which shows that Ag/AgBr/Fe 2 O 3 The functional fabric has good antibacterial activity on escherichia coli.
FIG. 4 shows the antibacterial properties of different functional fabrics irradiated with 360nm UV light for 60min, and it can be seen from the graph that the antibacterial rate of the original fabrics against bacteria and fungi is maintained at about 10%, almost negligible, and the fabrics exhibit excellent antibacterial rate after the photocatalyst is loaded, and Ag/AgBr/Fe 2 O 3 The antibacterial rate of the functional fabric to the escherichia coli reaches more than 90 percent.
To further prove Ag/AgBr/Fe 2 O 3 After being modified by Ag/AgBr, the photocurrent response is enhanced, and EIS tests are carried out on three materials according to the invention, and the results are shown in figure 5. FIG. 5 is Ag/AgBr, fe 2 O 3 、Ag/AgBr/Fe 2 O 3 The EIS Nyquist spectrograms of the three single photocatalysts can judge the charge transfer efficiency, and the larger the radius is, the larger the resistance is and the lower the electron transfer efficiency is. It can be seen that Fe 2 O 3 Compared with two single materials of Ag/AgBr, ag/AgBr/Fe 2 O 3 The radius of the arc is obviously reduced, which indicates that the surface plasma effect can induce the charge transfer resistance of the photocatalytic material to be greatly reduced and the electron transfer efficiency to be enhanced.
In the present invention, ag/AgBr/Fe 2 O 3 The antibacterial mechanism of the functional fabric is mainly characterized in that active species with strong oxidability such as hydroxyl free radicals, superoxide free radicals and the like are generated under the excitation of ultraviolet light, and the permeability of cell membranes is changed by destroying the cell walls of bacteria, so that the cells are damaged, and the cells are directly dead. Based on analysis of the above results, ag/AgBr/Fe 2 O 3 The functional fabric has good formaldehyde removal performance and antibacterial performance, can meet the requirements of people on the functional fabric, provides reference for the removal of outdoor formaldehyde and the protection of the fabric on human skin, and has important invention significance.
Claims (9)
1. The preparation method of the photocatalytic formaldehyde-removing antibacterial functional fabric is characterized by comprising the following steps of:
step one, fe 2 O 3 Preparation of functional fabrics
Modifying the polyester fabric by adopting NaOH solution under the water bath condition, then washing and drying the polyester fabric by deionized water, and adding the modified fabric into the polyester fabric containing Fe 2 O 3 The powder is stirred magnetically after being evenly dispersed in deionized water by ultrasonic, transferred into a polytetrafluoroethylene high-pressure reaction kettle, subjected to hydrothermal reaction, cooled to room temperature, and dried to prepare Fe 2 O 3 A functional fabric;
the volume mass ratio of the NaOH solution to the polyester fabric is (20-40) mL:1g; fe (Fe) 2 O 3 The concentration of the powder in deionized water is 5-15 mg/L;
step two, ag/AgBr/Fe 2 O 3 Preparation of functional fabrics
Fe prepared in step one by photochemical vapor deposition 2 O 3 Depositing Ag/AgBr on the surface of the functional fabric to prepare Ag/AgBr/Fe 2 O 3 A functional fabric; namely, the photocatalytic formaldehyde-removing antibacterial functional fabric is completed;
fe prepared in the first step by the photochemical vapor deposition method in the second step 2 O 3 The specific operation of depositing Ag/AgBr on the surface of the functional fabric is as follows:
fe is added to 2 O 3 Soaking functional fabric in AgNO 3 Adding KBr powder into the solution to perform light-proof reaction, then placing the solution under a xenon lamp for irradiation, washing the fabric with deionized water after the reaction is finished, and drying to prepare Ag/AgBr/Fe 2 O 3 A functional fabric; wherein AgNO 3 The concentration is 50-250 mg/L;
said Fe 2 O 3 The mass ratio of the functional fabric to KBr powder is 1: 0.05-0.15;
said Fe 2 O 3 Functional fabric and AgNO 3 The mass ratio of the solution is 1: 20-40.
2. The method for preparing the photocatalytic formaldehyde-removing antibacterial functional fabric according to claim 1, wherein the drying conditions in the first and second steps are as follows: after drying 12h in an oven at 60 ℃, the product is ready for use.
3. The method for preparing the photocatalytic formaldehyde-removing antibacterial functional fabric according to claim 1, wherein the AgNO 3 The concentration is 50mg/L, 100mg/L, 150mg/L, 200mg/L or 250mg/L.
4. The method for preparing the photocatalytic formaldehyde-removing antibacterial functional fabric according to claim 1, wherein the water bath condition in the first step is 60-80 ℃ for 40-60 min.
5. The method for preparing the photocatalytic formaldehyde-removing antibacterial functional fabric according to claim 1, characterized in that,
the time for uniformly dispersing the ultrasonic waves in the first step is 20-40 min.
6. The method for preparing the photocatalytic formaldehyde-removing antibacterial functional fabric according to claim 1, wherein the hydrothermal reaction condition in the step one is that the hydrothermal reaction is carried out for 2-4 hours at 80-100 ℃.
7. The method for preparing the photocatalytic formaldehyde-removing antibacterial functional fabric according to claim 1, characterized in that,
the drying conditions in step one were oven drying 12h at 60 ℃.
8. The method for preparing the photocatalytic formaldehyde-removing antibacterial functional fabric according to claim 1, characterized in that,
fe in step one 2 O 3 The concentration of the powder in deionized water is 10-15 mg/L.
9. The preparation method of the photocatalytic formaldehyde-removing antibacterial functional fabric according to claim 1, wherein the volume-mass ratio of the NaOH solution to the polyester fabric in the first step is (25-35) mL:1g.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101627267B1 (en) * | 2015-06-08 | 2016-06-03 | (주)서우 | The method of manufacturing the photocatalyst antibacterial fabric and the fabric by the method |
| CN106978715A (en) * | 2017-04-20 | 2017-07-25 | 武汉工程大学 | A kind of weaving cloth composite with photocatalysis and anti-microbial property and preparation method thereof |
| CN107537522A (en) * | 2017-09-25 | 2018-01-05 | 中国科学院广州地球化学研究所 | Composite of silver-colored silver halide load iron nano-mineral and preparation method thereof |
| WO2022125868A2 (en) * | 2020-12-10 | 2022-06-16 | Claros Technologies Inc. | Antimicrobial and antiviral nanocomposites sheets |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101627267B1 (en) * | 2015-06-08 | 2016-06-03 | (주)서우 | The method of manufacturing the photocatalyst antibacterial fabric and the fabric by the method |
| CN106978715A (en) * | 2017-04-20 | 2017-07-25 | 武汉工程大学 | A kind of weaving cloth composite with photocatalysis and anti-microbial property and preparation method thereof |
| CN107537522A (en) * | 2017-09-25 | 2018-01-05 | 中国科学院广州地球化学研究所 | Composite of silver-colored silver halide load iron nano-mineral and preparation method thereof |
| WO2022125868A2 (en) * | 2020-12-10 | 2022-06-16 | Claros Technologies Inc. | Antimicrobial and antiviral nanocomposites sheets |
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