CN110004705B - Preparation method of graphene-compounded fiber fabric with efficient photocatalytic function - Google Patents
Preparation method of graphene-compounded fiber fabric with efficient photocatalytic function Download PDFInfo
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- CN110004705B CN110004705B CN201910170093.5A CN201910170093A CN110004705B CN 110004705 B CN110004705 B CN 110004705B CN 201910170093 A CN201910170093 A CN 201910170093A CN 110004705 B CN110004705 B CN 110004705B
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- 239000004744 fabric Substances 0.000 title claims abstract description 96
- 239000000835 fiber Substances 0.000 title claims abstract description 49
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 41
- 239000002131 composite material Substances 0.000 claims abstract description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000006185 dispersion Substances 0.000 claims abstract description 26
- 239000010936 titanium Substances 0.000 claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 10
- 230000000694 effects Effects 0.000 claims abstract description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 53
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 38
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 19
- 229920000742 Cotton Polymers 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- 229960000583 acetic acid Drugs 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 229920000728 polyester Polymers 0.000 claims description 9
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- -1 n-propyl titanate Chemical compound 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 239000000271 synthetic detergent Substances 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 3
- 229910019931 (NH4)2Fe(SO4)2 Inorganic materials 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 29
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 29
- 241000894006 Bacteria Species 0.000 abstract description 14
- 238000004042 decolorization Methods 0.000 abstract description 13
- 241000588724 Escherichia coli Species 0.000 abstract description 11
- 230000002147 killing effect Effects 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 7
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 238000005470 impregnation Methods 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 29
- 230000001954 sterilising effect Effects 0.000 description 14
- 238000004659 sterilization and disinfection Methods 0.000 description 14
- 238000002791 soaking Methods 0.000 description 12
- 238000002835 absorbance Methods 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- 239000011941 photocatalyst Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 238000007146 photocatalysis Methods 0.000 description 8
- 239000004753 textile Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 238000001782 photodegradation Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- NAXKFVIRJICPAO-LHNWDKRHSA-N [(1R,3S,4R,6R,7R,9S,10S,12R,13S,15S,16R,18S,19S,21S,22S,24S,25S,27S,28R,30R,31R,33S,34S,36R,37R,39R,40S,42R,44R,46S,48S,50R,52S,54S,56S)-46,48,50,52,54,56-hexakis(hydroxymethyl)-2,8,14,20,26,32,38,43,45,47,49,51,53,55-tetradecaoxa-5,11,17,23,29,35,41-heptathiapentadecacyclo[37.3.2.23,7.29,13.215,19.221,25.227,31.233,37.04,6.010,12.016,18.022,24.028,30.034,36.040,42]hexapentacontan-44-yl]methanol Chemical compound OC[C@H]1O[C@H]2O[C@H]3[C@H](CO)O[C@H](O[C@H]4[C@H](CO)O[C@H](O[C@@H]5[C@@H](CO)O[C@H](O[C@H]6[C@H](CO)O[C@H](O[C@H]7[C@H](CO)O[C@@H](O[C@H]8[C@H](CO)O[C@@H](O[C@@H]1[C@@H]1S[C@@H]21)[C@@H]1S[C@H]81)[C@H]1S[C@@H]71)[C@H]1S[C@H]61)[C@H]1S[C@@H]51)[C@H]1S[C@@H]41)[C@H]1S[C@H]31 NAXKFVIRJICPAO-LHNWDKRHSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 229910019501 NaVO3 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 210000002429 large intestine Anatomy 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NZYCYASKVWSANA-UHFFFAOYSA-M new methylene blue Chemical compound [Cl-].CCNC1=C(C)C=C2N=C(C=C(C(NCC)=C3)C)C3=[S+]C2=C1 NZYCYASKVWSANA-UHFFFAOYSA-M 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 208000017983 photosensitivity disease Diseases 0.000 description 1
- 231100000434 photosensitization Toxicity 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 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
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B13/00—Treatment of textile materials with liquids, gases or vapours with aid of vibration
-
- 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
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
-
- 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
- D06M11/73—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 carbon or compounds thereof
- D06M11/74—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 carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- 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
- D06M11/77—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 silicon or compounds thereof
- D06M11/79—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 silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- 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
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention provides a preparation method of a fiber fabric with high-efficiency photocatalytic function composite graphene, which is characterized in that a multi-component high-activity composite graphene material is loaded on the fiber fabric with large surface area and good flexibility in batches by adopting an impregnation method, and the preparation method comprises the specific steps of respectively preparing a graphene oxide dispersion liquid, a titanium-based sol doped with elements and a silicon-based sol, and simultaneously selecting a proper fiber fabric and carrying out pretreatment; then immersing the clean fiber fabric into GO dispersion liquid for ultrasonic treatment; slowly adding the titanium-based sol and the silicon-based sol doped with elements under the ultrasonic condition; and finally, taking out the fiber fabric, and drying at 50-110 ℃ to solidify the composite catalyst on the fabric, thereby obtaining the fiber fabric finished by the composite graphene with the efficient photocatalytic function. The product has a decolorization rate of more than 98% for methylene blue aqueous solution under visible light, a killing rate of more than 99% for bacteria in water, and a killing rate of more than 98% for escherichia coli, and the photocatalytic function composite graphene in the sample is firmly combined with the fiber fabric.
Description
Technical Field
The invention relates to a graphene-compounded fiber fabric with a high-efficiency photocatalytic function and a preparation method thereof, and belongs to the technical field of novel inorganic non-metallic materials.
Technical Field
Photocatalysis for degrading environmental pollutants is a new technology which is being developed and perfected, but with TiO2Although the traditional photocatalysts represented by the general formula are stable in chemical property, safe to use and low in cost, the traditional photocatalysts need ultraviolet light with the wavelength of 387nm or less for excitation and generate photogenerated electrons (e)-) And photo-generated holes (h)+) Very easy recombination, low quantum efficiency of the photocatalytic reaction, no use of visible light, and even moreThe powdered photocatalyst is difficult to recover in waste water and waste gas treatment, etc., thus limiting the application of the technology. In response to these defects, various research and development works have been carried out at home and abroad, such as in TiO2In the modification aspect, precious metal deposition, compounding of a plurality of semiconductors, ion doping, photosensitization, surface reduction treatment and the like are adopted; in the aspect of coupling of photocatalysis and other technologies, microwave field-assisted photocatalysis, thermocatalysis and photocatalysis coupling, photocatalysis and electrocatalysis coupling and the like are adopted.
Graphene has excellent properties of high electron mobility, high Young's modulus, high strength, easiness in chemical functionalization and the like, and derivatives of graphene oxide, reduced graphene oxide and the like are available. Due to the special physical and chemical properties, the photocatalyst has become a novel material in the field of material science, and the problem faced by the traditional photocatalyst can be solved. Some researches show that the graphene or the derivative and the modified composite photocatalyst are loaded on some carrier materials (such as textiles, metal nets, porous ceramics and the like) through a physical or chemical method, so that the range of visible light utilization of the catalyst can be enlarged, the efficiency of photocatalytic pollution removal and sterilization is improved, and the product is more convenient for sewage and air purification in various occasions.
In recent years, there have been many reports, and a representative article is "graphene/TiO2Research on photocatalytic degradation of organic pollutants by composite materials is advanced (journal of chemical engineering, Vol.67No. 5). The graphene is considered as a novel carbon nano material, has an ultra-large specific surface area and excellent conductivity, and is prepared by mixing the graphene with TiO2The composite material can obviously improve the photocatalytic performance of the composite material, and has wide application prospect in the field of photocatalysis. This article introduces graphene/TiO2Preparation method of composite nano material and application thereof in photocatalytic degradation of organic pollutants, and graphene/TiO is analyzed2The composite material promotes the photocatalysis mechanism, and finally, graphene/TiO is treated2The future development trend of the composite photocatalyst is shown. The related invention patents are also more, such as:
CN109092279A discloses a high-efficiency cellulose-based graphene/TiO2Composite photocatalysisCarbonizing cellulose, soaking in Ni solution, drying, graphitizing at high temperature, oxidizing by Hummers method, ultrasonic dispersing in water solution, and sequentially adding H3BO3And (NH)4)2TiF6Hydrolyzing, and calcining at a certain temperature to obtain the cellulose-based graphene/TiO2A composite photocatalyst is provided. The cellulose-based graphene/TiO is prepared by taking cellulose as a raw material through catalytic graphitization, oxidation, deposition and reduction2Composite photocatalysts, but at high cost. The photocatalyst has extremely high photocatalytic activity, can completely degrade a 10mg/L methyl orange solution within 8 minutes under the irradiation of ultraviolet light, and can reduce Cr (VI) with the concentration of 0.2mmol/L into Cr within 30 minutes3+。
CN106040311A discloses a textile fiber/graphene/FeVO4The preparation method of the composite environmental catalytic material comprises the following steps: soaking textile fibers into saturated dispersion liquid of graphene oxide, drying, cleaning, placing in a reducing agent solution, reacting at 50-80 ℃ for 0.5-1 h, cleaning, and drying to obtain textile fibers/graphene; adding textile fibers/graphene to Fe (NO)3)3And Na3PO4Stirring the solution, and then adding NaVO3And carrying out hydrothermal reaction on the mixture and urea at 120-180 ℃ for 3-8 h, cooling, washing and drying to obtain textile fiber/graphene/FeVO4A composite environmental catalytic material. The catalyst is easy to fall off and is easy to be limited in practical use.
CN109043681A discloses a graphene antibacterial fiber body-shaping underwear which does not have the defect that the one-piece underwear is inconvenient to go to a toilet, does not roll upwards, and has the characteristics of comfort and convenience in wearing and good shaping effect; and the fabric is made of europium-doped graphene antibacterial fiber cloth, has a good antibacterial effect, and is sanitary and safe to wear next to the skin.
Disclosure of Invention
The purpose of the invention is as follows: aims to provide graphene/composite TiO with visible light response catalysis function2Fiber fabric material and preparation thereof, making it responsive to visible lightThe range of the method is large, the activity of removing organic pollutants in wastewater and air and killing bacteria is high, the use is convenient, the use period is long, the cost is low, and the like, so that the practical application of the photocatalysis technology in environmental pollution treatment is promoted.
The technical scheme of the invention is as follows: a fiber fabric with efficient photocatalytic function and composite graphene and a preparation method thereof are disclosed, wherein a dipping method is adopted to load multi-component high-activity composite graphene materials on a fiber fabric with large surface area and good flexibility in batches, and the preparation method comprises the specific steps of firstly preparing GO dispersion liquid, titanium-based sol doped with elements and silicon-based sol respectively, and simultaneously selecting the fiber fabric and carrying out pretreatment; then immersing the clean fiber fabric into GO dispersion liquid for ultrasonic treatment; slowly adding the titanium-based sol and the silicon-based sol doped with elements under the ultrasonic condition; and finally, taking out the fiber fabric, and drying at 50-110 ℃ to solidify the composite catalyst on the fabric, thereby obtaining the fiber fabric finished by the composite graphene with the efficient photocatalytic function.
GO dispersion was prepared using a modified Hummers method: under low temperature and stirring conditions in concentrated H2SO4Adding flake graphite powder, then respectively and slowly adding a strong oxidant and deionized water, continuously stirring, adding a reducing agent at a medium temperature, filtering when the reaction solution is hot after the reaction solution becomes bright yellow, respectively washing with dilute acid and deionized water until the filtrate is neutral, and then dispersing the obtained graphite oxide in the deionized water and dispersing under an ultrasonic condition to obtain the GO dispersion liquid.
The strong oxidant adopted in the preparation of GO dispersion is K2Cr2O7、KClO3、KMnO4And HClO, the reducing agent is Na2S2O3、(NH4)2Fe(SO4)2Ascorbic acid and H2O2The diluted acid is HCl and acetic acid, wherein the mass ratio of the raw materials is as follows: the ratio of the flake graphite powder to the concentrated sulfuric acid to the oxidant to the reducing agent to the dilute acid to the deionized water is 1.5-2.5: 90-100: 2.8-3.6: 2.5-3.2: 0.02-0.2: 350-450.
Further, preparing titanium-based sol doped with elements: slowly adding titanate into anhydrous ethanol and iceObtaining a solution A in a mixed solution of acetic acid; dissolving nitrate of the doped element in absolute ethyl alcohol and deionized water to obtain a solution B; and slowly dripping the solution A into the solution B in the ice water bath, and continuously stirring to obtain the doped titanium-based sol. When preparing the titanium-based sol doped with elements, the mass ratio of the solution A is as follows: titanate, absolute ethyl alcohol and glacial acetic acid are 11.5-23.0: 51.9-65.1: 0.7-7.1, and the adopted titanate is n-propyl titanate or n-butyl titanate; the mass ratio of the solution B is as follows: doping elements of nitrate, absolute ethyl alcohol and deionized water are 0.2-0.8: 14.8-26.1: 0.7-3.5, and the adopted doping elements are nitrates of La, Ce, Pm, Sm and other elements; finally obtaining the doped TiO2And (3) sol.
Preparing a silicon-based sol: slowly adding orthosilicate into the mixed solution of absolute ethyl alcohol, deionized water and dilute acid, and uniformly stirring and mixing, wherein the mass ratio of the orthosilicate is as follows: orthosilicate ester, absolute ethyl alcohol, deionized water and dilute acid, wherein the ratio of the orthosilicate ester to the absolute ethyl alcohol to the deionized water to the dilute acid is 4.5-4.8: 9.2-11.8: 1.5-2.0: 0.02-0.04; the adopted silicate is ethyl orthosilicate or propyl orthosilicate, and the adopted dilute acid is HCl, acetic acid and the like; to obtain SiO2And (3) sol.
The adopted fiber fabric is pure cotton fabric or polyester cotton fabric, and the fiber fabric needs to be boiled by NaOH and synthetic detergent solution in advance, neutralized by glacial acetic acid, washed to be neutral and dried for later use.
The GO dispersion liquid, the doped element titanium-based sol and the silica sol are loaded on the fiber fabric by adopting an impregnation method step by step: in an ultrasonic oscillation system, firstly placing a pretreated flaky fiber fabric in GO dispersion liquid, then slowly adding element-doped titanium-based sol and silicon-based sol, finally taking out the fabric, drying at a specific temperature and curing the composite catalyst.
Loading graphene oxide, doped element titanium-based sol and silicon-based sol on a fiber fabric by adopting step-by-step implementation, wherein the mass ratio of the used main raw materials is as follows: the ratio of GO dispersion liquid to doped element titanium-based sol to silicon-based sol to fiber fabric is 403.2-458.6: 93.4-109.1: 14.3-18.9: 30.4-250.1.
The invention has the beneficial effects that: according to the invention, under the process conditions of strictly selecting raw materials and concentration ratio, ultrasonic intensity and ultrasonic time, temperature and solution pH in each time period and the like, the graphene composite fiber fabric with the efficient photocatalytic function is prepared, and a very obvious effect is obtained. Firstly, the photocatalytic efficiency of organic pollutant degradation is greatly improved; secondly, the catalyst widens the response range to visible light; and thirdly, a fiber fabric with large surface area and good flexibility is selected as a carrier of the high-activity composite graphene, so that the high-activity composite graphene is firmly combined and has long service cycle. Therefore, the invention can promote the utilization of the sun to treat the waste gas and the waste water, and can generate good economic and social benefits. The product has a decolorization rate of more than 98% for methylene blue aqueous solution under visible light, a killing rate of more than 99% for bacteria in water and a killing rate of more than 98% for escherichia coli, the prepared sample has firm combination of the photocatalytic function composite graphene and fiber fabric, and the decolorization rate of the methylene blue aqueous solution is almost unchanged after the product is repeatedly used for 10 times.
Detailed Description
1. Preparation and pretreatment of the desired materials
(1) GO dispersion was prepared using a modified Hummers method: adding flake graphite powder into concentrated H under low temperature and stirring state2SO4And then respectively and slowly adding a strong oxidant and deionized water, continuously stirring, adding a reducing agent at a medium temperature, filtering while hot after the reaction solution becomes bright yellow, respectively washing with dilute acid and deionized water until the filtrate is neutral, and then dispersing the obtained graphite oxide in the deionized water and dispersing under an ultrasonic condition to obtain the GO dispersion liquid. Wherein the oxidant used is KClO3Or KMnO4The reducing agent is ascorbic acid and H2O2The dilute acid is dilute hydrochloric acid or acetic acid, etc.
(2) Preparing titanium-based sol doped with elements: slowly adding titanate into a mixed solution of absolute ethyl alcohol and glacial acetic acid to obtain a solution A; dissolving nitrate of the doped element in absolute ethyl alcohol and deionized water to obtain a solution B; slowly dropwise adding the solution A into a solution B placed in an ice water bath, and continuously stirring to obtain doped TiO2And (3) sol. The titanate and the doped element nitrate used in the method are of specific types and the raw materials used in the method are allIn a certain proportion.
(3) Preparing a silicon-based sol: slowly adding orthosilicate into the mixed solution of absolute ethyl alcohol, deionized water and dilute acid, and uniformly stirring and mixing to obtain SiO2And (3) sol. Wherein the silicate is tetraethoxysilane or propyl orthosilicate, and the mass ratio of the raw materials is as follows: the ratio of the orthosilicate ester, the absolute ethyl alcohol, the deionized water and the dilute acid is 4.5-4.8: 9.2-11.8: 1.5-2.0: 0.02-0.04.
(4) Selecting a fiber fabric and pretreating: the fiber fabric is pure cotton fabric or polyester cotton fabric, or various blended fabrics of natural fiber and artificial fiber, and is prepared by mixing the fabric with alkali (such as Na)2CO3NaOH, etc.) and synthetic detergent solution, then neutralizing with glacial acetic acid, washing with water to neutrality (pH value is 6.5-7.5), and drying for later use.
2. The loading of various components on the fiber fabric is carried out step by adopting an impregnation method
(1) And immersing the pretreated fiber fabric into a graphene oxide solution for ultrasonic treatment.
(2) Under the ultrasonic condition, slowly adding titanium-based sol doped with elements.
(3) Under the ultrasonic condition, the silicon-based sol is slowly added.
(4) And finally, taking out the fabric, drying the fabric at 50-110 ℃ and curing the composite catalyst to obtain the required product.
3. Characterization of physical and chemical properties of the product
(1) Measuring the absorption range of the sample to light with an ultraviolet-visible diffuse reflectance spectrometer according to EgThe band gap of the semiconductor is estimated by the 1240/λ equation.
(2) Methylene blue light degradation decolorization rate: respectively putting an unloaded polyester-cotton fabric and a loaded fabric into 2 culture dishes, respectively adding 50ml of methylene blue solution with the concentration of 20mg/l, placing the culture dishes under a 20W fluorescent lamp for illumination (the wavelength is 400-760 nm), enabling the liquid level to be 25cm away from the center of a light source, sampling at different times, measuring the absorbance change of the methylene blue solution at the wavelength of 650nm by using an ultraviolet-visible spectrophotometer, and drawing by using the relation between the variation of the absorbance of the solution and the illumination time to obtain the decolorization rate of the methylene blue at different time periods, thereby representing the photocatalytic activity of the fabric.
(3) And (3) sterilization test: the bacteria killing effect of the sample is measured according to a flat plate method in national standard GB5750-85 Drinking Water Standard test method, and the bacteria killing rate of the large intestine rod is measured according to a multi-tube fermentation method in the standard.
(4) Washing fastness: according to GB/T3921-2008 soaping-resistant color fastness of textile color fastness test, 30 times of soaping are respectively carried out on the finished fabrics, and the washability of the finished fabrics is evaluated through the absorbance change of methyl blue solution before and after illumination.
(5) The repeated service life is as follows: and (3) after the fabric is put into the methylene blue solution for the first test, taking out the fabric and putting into a new methylene blue solution again for the second test, repeating the steps for a plurality of times, and inspecting the service life of the fabric.
Example 1: ce doped TiO2/SiO2Preparation and performance of/GO/polyester cotton cloth
Ce-doped TiO is prepared according to the embodiment2/SiO240 pieces of/GO/polyester cotton cloth, and the preparation method and the detection result of the sample are as follows:
(1) preparing a GO dispersion: 60ml of concentrated sulfuric acid is added into a three-neck flask in an ice-water bath, 2.5g of graphite powder is added under stirring, and the mixture is stirred for 15 hours at room temperature. Slowly adding 4g of potassium permanganate, controlling the reaction temperature to be not more than 10 ℃, after 20min, heating to 50 ℃, continuing to stir for 3h, slowly adding 110ml of deionized water, continuing to stir for 20min, heating to 90 ℃, adding 12ml of hydrogen peroxide with the mass fraction of 30%, filtering after the reaction solution turns bright yellow, and washing the filtrate to be neutral by using 5% HCl solution and deionized water. And dispersing the obtained graphite oxide in 300ml of aqueous solution, and dispersing for 1h under the ultrasonic condition to obtain a stable GO dispersion liquid.
(2) Preparation of Ce-doped TiO2Sol: slowly adding n-butyl titanate into a mixed solution of anhydrous ethanol and glacial acetic acid, wherein the ratio of the n-butyl titanate to the anhydrous ethanol to the glacial acetic acid is 17.5: 62.1: 3.7, so as to obtain a solution A; adding Ce (NO)3)3·6H20 in absolute ethanol and deionized water, and its Ce (NO)3)3·6H20: absolute ethyl alcohol: deionized water 0.5: 20.8: 2.1 to obtain solution B; and slowly dropwise adding the solution A into the solution B in an ice water bath.
(3) Preparation of SiO2Sol: slowly adding 5ml of tetraethoxysilane into a mixed solution of 15ml of absolute ethyl alcohol, 2ml of deionized water and 0.05ml of HCl, magnetically stirring for 2 hours, and uniformly mixing.
(4) Pretreating a polyester-cotton fabric: cutting the polyester cotton fabric into test sample blocks of 100mm multiplied by 40mm, boiling for 30min at 80-90 ℃ by using NaOH with the concentration of 5g/l and synthetic detergent with the concentration of 4g/l, neutralizing by using glacial acetic acid, washing to be neutral by using water, and drying for later use at 90 ℃.
(5) Step-by-step implementation of GO dispersion and Ce-doped TiO2Sol and SiO2Loading the sol on polyester cotton cloth: dipping 40 pretreated polyester cotton cloth blocks of 100mm multiplied by 40mm into 300ml of GO dispersion liquid, and carrying out ultrasonic treatment for 1.5 h; then slowly dropping 50ml Ce-doped TiO under the ultrasonic condition2Sol, controlling the temperature to be about 65 ℃, and carrying out ultrasonic treatment for 2 hours; then slowly dropping 19.7ml of SiO under the ultrasonic condition2Sol, and continuing ultrasonic treatment for 2 hours at 65 ℃; and finally, taking out the fabric, drying the fabric at 80 ℃ for 5min, and curing the fabric at 120 ℃ for 1h to obtain the product.
(6) Results of sample testing
Ultraviolet-visible diffuse reflection spectrometer tests show that the strong absorption range of a sample to light exceeds 510nm, the side bands extend to 650nm, and the absorption range is determined according to EgThe band gap was reduced to around 2.0eV, estimated as 1240/λ.
The photodegradation test shows that the decolorization rate of the methylene blue reaches 98 percent under the irradiation of visible light for 8 hours.
And thirdly, the 24-hour soaking sterilization test shows that when the total number of bacteria in the water sample is 2900/ml and the total number of escherichia coli is 790 per 100ml, the sterilization rate of the water sample on the bacteria reaches over 99 percent, and the sterilization rate on the escherichia coli is more than 95 percent.
The fastness to washing test shows that: the absorbance of the methylene blue solution soaked in the unloaded fabric is almost unchanged, the degradation rate of the methylene blue solution soaked in the loaded fabric on the methylene blue is 95%, and after 30 times of washing, the degradation rate still reaches 94.3%, which indicates that the loading fastness is strong and the washability is good.
The service life test shows that: after the sample is repeatedly used for 10 times, the color of the methylene blue solution is almost completely faded after the sample is irradiated by visible light for 8 hours, which shows that the prepared photocatalytic coating fabric can be repeatedly used and has long service life.
Example 2: ce doped TiO2Preparation and Properties of/GO/polyester-Cotton cloth (also make 40 pieces)
SiO was not prepared except for step (3) in example 12Sol and step (5) no SiO loading2The procedure was the same as in example 1 except for the sol. The test results for the samples were as follows:
ultraviolet-visible diffuse reflection spectrometer tests show that the absorption range of a sample to light is over 510nm, and the side band is extended to 650 nm.
② the photodegradation test shows that under the irradiation of visible light for 8h, the decolorization rate of the methylene blue is 92%.
And thirdly, the 24-hour soaking sterilization test shows that when the total number of bacteria in the water sample is 2900/ml and the total number of escherichia coli is 790 per 100ml, the sterilization rate of the water sample on the bacteria is more than 95 percent, and the sterilization rate of the water sample on the escherichia coli is more than 90 percent.
The fastness to washing test shows that: the absorbance of the methylene blue solution for soaking the unloaded fabric is almost unchanged, and the degradation rate of the methylene blue by the absorbance of the methylene blue solution for soaking the loaded fabric is 92%. After 30 times of washing, the degradation rate still reaches 91.5 percent, which indicates good washing fastness.
The service life test shows that: after the load fabric is repeatedly used for 10 times, the decolorization rate of the methylene blue solution is only reduced by 3.5% after the load fabric is irradiated by visible light for 8 hours, which shows that the prepared photocatalytic coating fabric can be repeatedly used and has longer service life.
Example 3: ce doped TiO2/SiO2Preparation and Properties of polyester-cotton cloth (also make 40 pieces)
The procedure was the same as in example 1 except that no GO dispersion was prepared in step (1) and no GO-supported dispersion was prepared in step (5) in example 1. The test results for the samples were as follows:
ultraviolet-visible diffuse reflection spectrometer tests show that the absorption range of a sample to light is over 500nm, and the side bands are expanded to 630 nm.
② the photodegradation test shows that under the irradiation of visible light for 8h, the decolorization rate of the methylene blue is 88%.
And thirdly, the 24-hour soaking sterilization test shows that when the total number of bacteria in the water sample is 2900/ml and the total number of escherichia coli is 790 per 100ml, the sterilization rate of the water sample on the bacteria is more than 90 percent, and the sterilization rate of the water sample on the escherichia coli is more than 85 percent.
The fastness to washing test shows that: the absorbance of the methylene blue solution for soaking the unloaded fabric is almost unchanged, and the degradation rate of the methylene blue by the absorbance of the methylene blue solution for soaking the loaded fabric is 92%. After 30 times of washing, the degradation rate still reaches 91.5 percent, which indicates good washing fastness.
The service life test shows that: after the load fabric is repeatedly used for 10 times, the decolorization rate of the methylene blue solution is only reduced by 3.5% after the load fabric is irradiated by visible light for 8 hours, which shows that the prepared photocatalytic coating fabric can be repeatedly used and has longer service life.
Example 4: TiO 22/SiO2Preparation and Properties of/GO/polyester-Cotton cloth (also make 40 pieces)
Preparation of Ce-doped TiO according to example 1 except for step (2)2Without adding Ce (NO) to the sol3)3·6H2Except for 0, the other operation steps were the same as in example 1. The test results for the samples were as follows:
ultraviolet-visible diffuse reflection spectrometer tests show that the absorption range of a sample to light is over 510nm, and the side band is extended to 650 nm.
② the photodegradation test shows that under the irradiation of visible light for 8h, the decolorization rate of the methylene blue is 92%.
And thirdly, the 24-hour soaking sterilization test shows that when the total number of bacteria in the water sample is 2900/ml and the total number of escherichia coli is 790 per 100ml, the sterilization rate of the water sample on the bacteria is more than 95 percent, and the sterilization rate of the water sample on the escherichia coli is more than 90 percent.
The fastness to washing test shows that: the absorbance of the methylene blue solution for soaking the unloaded fabric is almost unchanged, and the degradation rate of the methylene blue by the absorbance of the methylene blue solution for soaking the loaded fabric is 92%. After 30 times of washing, the degradation rate still reaches 91.5 percent, which indicates good washing fastness.
The service life test shows that: after the load fabric is repeatedly used for 10 times, the decolorization rate of the methylene blue solution is only reduced by 3.5% after the load fabric is irradiated by visible light for 8 hours, which shows that the prepared photocatalytic coating fabric can be repeatedly used and has longer service life.
The above examples show that the GO dispersion, Ce doped TiO was impregnated by impregnation2Sol and SiO2The sol is loaded on polyester cotton cloth step by step (see example 1), and the product has very high photocatalytic decolorization efficiency on representative methylene blue organic matters and also has very high activity on killing bacteria and escherichia coli; and the products such as GO (see example 2) and SiO are absent2(see example 3) and doping element Ce (see example 4), the photocatalytic and bactericidal activity of the product is reduced to different degrees, but the binding fastness of the composite prepared in all the examples to the polyester-cotton cloth and the service life of the sample are not changed greatly.
Claims (5)
1. A preparation method of a fiber fabric with high-efficiency photocatalytic function composite graphene is characterized in that a dipping method is adopted to load multi-component high-activity composite graphene materials on a fiber fabric with large surface area and good flexibility in batches, and the preparation method comprises the specific steps of firstly respectively preparing graphene oxide dispersion liquid, element-doped titanium-based sol and silicon-based sol, and simultaneously selecting proper fiber fabric and carrying out pretreatment; then immersing the clean fiber fabric into GO dispersion liquid for ultrasonic treatment; slowly adding the titanium-based sol and the silicon-based sol doped with elements under the ultrasonic condition; finally, taking out the fiber fabric, and drying at the temperature of 50-110 ℃ to solidify the composite graphene material on the fiber fabric, so as to obtain the fiber fabric finished by the composite graphene with the efficient photocatalytic function;
GO dispersion was prepared using a modified Hummers method: at low temperature and under stirring in concentrated H2SO4Adding flake graphite powder, and dividingRespectively and slowly adding a strong oxidant and deionized water, continuously stirring, adding a reducing agent at a medium temperature, filtering while hot after the reaction solution turns to bright yellow, respectively washing with dilute acid and deionized water until the filtrate is neutral, and dispersing the obtained graphene oxide in the deionized water and dispersing under an ultrasonic condition to obtain a GO dispersion liquid;
the strong oxidant adopted in the preparation of GO dispersion is K2Cr2O7、KClO3、KMnO4 And HClO, the reducing agent is Na2S2O3、(NH4)2Fe(SO4)2Ascorbic acid and H2O2 The diluted acid is HCl and acetic acid, wherein the mass ratio of the raw materials is as follows: flake graphite powder, concentrated sulfuric acid, an oxidant, a reducing agent, dilute acid and deionized water are 1.5-2.5: 90-100: 2.8-3.6: 2.5-3.2: 0.02-0.2: 350-450;
preparing titanium-based sol doped with elements: slowly adding titanate into a mixed solution of absolute ethyl alcohol and glacial acetic acid to obtain a solution A; dissolving nitrate of the doped element in absolute ethyl alcohol and deionized water to obtain a solution B; and slowly dripping the solution A into the solution B in the ice water bath, and continuously stirring to obtain the titanium-based sol doped with the elements.
2. The method according to claim 1, wherein the titanium-based sol doped with the element is prepared by mixing the solution A in the following mass ratio: titanate, absolute ethyl alcohol and glacial acetic acid are = 11.5-23.0: 51.9-65.1: 0.7-7.1, and the adopted titanate is n-propyl titanate or n-butyl titanate; the mass ratio of the solution B is as follows: nitrate of doping elements, absolute ethyl alcohol and deionized water are = 0.2-0.8: 14.8-26.1: 0.7-3.5, and the adopted doping elements are nitrate of La, Ce, Pm and Sm; finally obtaining the doped TiO2And (3) sol.
3. The method according to claim 1, wherein the silica-based sol is prepared by: slowly adding orthosilicate into the mixed solution of absolute ethyl alcohol, deionized water and dilute acid, and uniformly stirring and mixing, wherein the mass ratio of the orthosilicate is as follows: ortho silicate ester ofThe ratio of the water to the ethanol to the deionized water to the dilute acid is 4.5-4.8: 9.2-11.8: 1.5-2.0: 0.02-0.04; the adopted silicate is ethyl orthosilicate or propyl orthosilicate, and the adopted dilute acid is HCl and acetic acid to obtain SiO2And (3) sol.
4. The preparation method of claim 1, wherein the fiber fabric is pure cotton fabric or polyester cotton fabric, and the fiber fabric is boiled with NaOH and synthetic detergent solution, neutralized with glacial acetic acid, washed with water to neutral, and dried for use.
5. The preparation method of claim 1, wherein the loading of the graphene oxide, the doped element titanium-based sol and the silicon-based sol on the fiber fabric is carried out step by step, and the mass ratio of the raw materials is as follows: GO dispersion liquid, doped element titanium-based sol, silicon-based sol and fiber fabric = 403.2-458.6: 93.4-109.1: 14.3-18.9: 30.4-250.1.
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