CN114318856B - Antibacterial fiber, preparation method and application - Google Patents
Antibacterial fiber, preparation method and application Download PDFInfo
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- CN114318856B CN114318856B CN202011075056.5A CN202011075056A CN114318856B CN 114318856 B CN114318856 B CN 114318856B CN 202011075056 A CN202011075056 A CN 202011075056A CN 114318856 B CN114318856 B CN 114318856B
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- metal carbide
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- 239000000835 fiber Substances 0.000 title claims abstract description 113
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000004744 fabric Substances 0.000 claims abstract description 139
- 238000000576 coating method Methods 0.000 claims abstract description 95
- 239000011248 coating agent Substances 0.000 claims abstract description 91
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 91
- 150000003624 transition metals Chemical class 0.000 claims abstract description 64
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 43
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 43
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 29
- 239000002086 nanomaterial Substances 0.000 claims abstract description 17
- 239000002135 nanosheet Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 230000000845 anti-microbial effect Effects 0.000 claims abstract description 6
- 229910001451 bismuth ion Inorganic materials 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims description 94
- 229920000742 Cotton Polymers 0.000 claims description 77
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical group C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 61
- 238000003756 stirring Methods 0.000 claims description 37
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 36
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 36
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical group Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 claims description 34
- -1 polydimethylsiloxane Polymers 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
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- 239000002243 precursor Substances 0.000 claims description 12
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
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- 229920002334 Spandex Polymers 0.000 claims description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N acrylaldehyde Natural products C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 5
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
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- 150000003839 salts Chemical group 0.000 claims description 3
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
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- 239000010955 niobium Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims 2
- 239000004599 antimicrobial Substances 0.000 abstract description 2
- 241000219146 Gossypium Species 0.000 description 69
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- 229910021641 deionized water Inorganic materials 0.000 description 8
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- 238000004626 scanning electron microscopy Methods 0.000 description 8
- 239000003242 anti bacterial agent Substances 0.000 description 7
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- 229940073609 bismuth oxychloride Drugs 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 5
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 5
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 4
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 4
- CBACFHTXHGHTMH-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-phenyl-2-piperidin-1-ylacetate;dihydrochloride Chemical compound Cl.Cl.C1CCCCN1C(C=1C=CC=CC=1)C(=O)OCCN1CCCCC1 CBACFHTXHGHTMH-UHFFFAOYSA-N 0.000 description 4
- 229910039444 MoC Inorganic materials 0.000 description 4
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 4
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- 238000006243 chemical reaction Methods 0.000 description 4
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- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 4
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 4
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- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- 108010077805 Bacterial Proteins Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- IPNGSXQUQIUWKO-UHFFFAOYSA-N bismuth;fluoro hypofluorite Chemical compound [Bi].FOF IPNGSXQUQIUWKO-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses an antibacterial fiber, which comprises a fabric fiber and an antibacterial coating coated on the outer surface of the fabric fiber, wherein the antibacterial coating comprises transition metal carbide and bismuth oxyhalide; the transition metal carbide is in a layered nano structure or a sheet nano structure, and the bismuth oxyhalide is in a nano sheet array and distributed on the surface of the transition metal carbide; bismuth ions in the bismuth oxyhalide and the transition metal carbide are adsorbed and combined through electrostatic force, and a heterogeneous interface is formed between the bismuth oxyhalide and the transition metal carbide. Also disclosed is a method for preparing an antimicrobial fiber, comprising: pretreating fabric fibers; preparing transition metal carbide; preparing a transition metal carbide coating; preparing a bismuth oxyhalide-transition metal carbide coating; hydrophobic coating preparation may also be included. The bismuth oxyhalide-transition metal carbide coating is formed on the surface of the fabric fiber at normal temperature, so that the fabric is endowed with rapid antibacterial capability on the basis of not damaging the comfort and safety of the fabric.
Description
Technical Field
The invention belongs to the technical field of material engineering, and particularly relates to an antibacterial fiber, a preparation method and application thereof.
Background
With the improvement of quality of life, people pay more attention to self-health management, and the performance of fabrics becomes a focus of attention. Especially medical staff's fabric, bacterial contamination can occur within hours, allowing bacteria to spread rapidly between patients, causing cross-infection between patients. At present, the antibacterial fabric mainly adopts traditional silver or silver ion, quaternary ammonium organic antibacterial agents and natural antibacterial agents. Silver and silver ion antibacterial agents can cause toxicity to the environment and human body, the stability of the organic antibacterial agents is poor, potential physiological effects can be caused to the human body, and the antibacterial effect of the natural antibacterial agents is poor. In addition, the antibacterial agents have long-time and poor sterilization effect, so that the development of the safe sterilizing agent with rapid sterilization and hydrophobicity has potential research value.
Recently, by exogenous excitation, the material can generate photo-heat and light motion, wherein the photo-heat can effectively destroy bacterial films and accelerate bacterial death. The free radicals generated by the light can cause oxidative damage to the bacteria, affect the metabolism of the bacteria, and reduce the activity of the bacteria. The synergistic effect of photo-thermal and photo-dynamic can kill bacteria and bacteria efficiently and rapidly in a short time, and meanwhile, the sterilization mode has spectrum antibacterial property. The fabric inevitably contacts with sunlight, so that sterilization by sunlight is necessarily the optimal choice of antibacterial fabric.
Bismuth oxybromide (BiOBr) is an indirect bandgap semiconductor with a suitable visible light responsive bandgap and exhibits good photocatalytic performance. However, the transfer rate of the photo-generated carriers of the single BiOBr is low and the recombination rate is high. In addition, the conduction band potential is low, which is unfavorable for the reduction of photo-generated electrons to generate superoxide radicals, thus limiting the improvement of the photocatalytic activity. Bismuth oxybromide has no photothermal effect under visible light due to poor light absorption, and these limitations limit its further application. Titanium carbide is a novel two-dimensional layered material, has excellent conductivity and light absorption capacity, and the excellent photo-thermal conversion efficiency expands the further application of the material, but the use of photo-thermal sterilization by only titanium carbide alone requires a long time at a very high temperature, which may affect the durability of the fabric. In addition, titanium carbide is extremely unstable in air and is easily oxidized into titanium dioxide by water in the air, so that the photo-thermal property of the material is reduced.
The above prior art has the following disadvantages;
1. the antibacterial fabric is sterilized by traditional ion release, has poor biological safety and can cause potential toxicity to human bodies;
2. the cost of the antibacterial fabric is high, the antibacterial effect is poor, and the time is long;
3. The antibacterial coating mostly adopts conditions such as high temperature and the like, so that the original performance of the fabric is affected;
4. the single use of bismuth oxybromide or titanium carbide as an antibacterial agent is poor in effect and unstable.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an antibacterial fiber, wherein the antibacterial fiber forms a bismuth oxyhalide-transition metal carbide-hydrophobic antibacterial coating on the surface of the fiber under the normal temperature condition, so that the fabric is endowed with rapid antibacterial capability on the basis of not damaging the comfort and safety of the fabric, and the antibacterial performance comprises sterilization and bacteriostasis.
The invention is realized by the following technical scheme:
An antibacterial fiber comprises a fabric fiber and an antibacterial coating coated on the outer surface of the fabric fiber, wherein the antibacterial coating comprises transition metal carbide and bismuth oxyhalide; the transition metal carbide is in a layered nano structure or a sheet nano structure, and bismuth oxyhalide is distributed on the surface of the transition metal carbide in a nano sheet array form; bismuth ions in the bismuth oxyhalide and the transition metal carbide are adsorbed and combined through electrostatic force, and a heterogeneous interface is formed between the bismuth oxyhalide and the transition metal carbide; the load capacity of the transition metal carbide nano-sheet on the fiber is 0.5-1.5 mg/cm 2, and the load capacity of the bismuth oxyhalide on the fiber is 0.5-1.5 mg/cm 2.
The fabric fiber is made of one or more of cotton, terylene, chinlon, spandex, acrylon or silk;
the transition metal carbide is one or more of titanium carbide, niobium carbide, vanadium carbide, tantalum carbide or molybdenum carbide;
The bismuth oxyhalide is one or more of bismuth oxychloride, bismuth oxybromide or bismuth oxyiodide.
In the technical scheme, when the transition metal carbide is of a layered nano structure, the number of layers is 1-5.
In the above technical solution, the size of the transition metal carbide is 1-5 μm.
In the technical scheme, the size of the bismuth oxyhalide is 300-800 nm.
An antibacterial fiber comprises a fabric fiber, an antibacterial coating coated on the outer surface of the fabric fiber and a hydrophobic layer coated outside the antibacterial coating, wherein the antibacterial coating comprises transition metal carbide and bismuth oxyhalide; the transition metal carbide is in a layered nano structure or a sheet nano structure, and bismuth oxyhalide is distributed on the surface of the transition metal carbide in a nano sheet array form; bismuth ions in the bismuth oxyhalide and the transition metal carbide are adsorbed and combined through electrostatic force, and a heterogeneous interface is formed between the bismuth oxyhalide and the transition metal carbide; the load capacity of the transition metal carbide nano-sheet on the fiber is 0.5-1.5 mg/cm 2, and the load capacity of the bismuth oxyhalide on the fiber is 0.5-1.5 mg/cm 2;
the fabric fiber is made of one or more of cotton, terylene, chinlon, spandex, acrylon or silk;
the transition metal carbide is one or more of titanium carbide, niobium carbide, vanadium carbide, tantalum carbide or molybdenum carbide;
The bismuth oxyhalide is one or more of bismuth oxyfluoride, bismuth oxychloride, bismuth oxybromide or bismuth oxyiodide;
The hydrophobic layer is one or more of polydimethylsiloxane, hexadecyl trimethoxy silane or tetraethoxysilane, and the thickness is 10-80 nm.
Another object of the present invention is to provide a method for preparing an antibacterial fiber.
A method for preparing an antibacterial fiber, comprising the following steps:
step one, pretreatment of fabric fibers:
Placing the fabric fibers in alkaline solution with pH of 11-13, soaking for more than 2 hours, washing the soaked fabric fibers to remove residual alkali, and drying to obtain pretreated fabric fibers;
the fabric fiber is made of one or more of cotton, terylene, chinlon, spandex, acrylon or silk;
Step two, preparing transition metal carbide:
placing transition metal aluminum carbide in hydrofluoric acid solution, stirring at 30-40 ℃, washing and drying the soaked transition metal aluminum carbide to obtain transition metal carbide;
The concentration of the hydrofluoric acid solution is 20-40 wt% and the lithium ion content is 30-50 mg/mL;
The transition metal is one or more of titanium, niobium, vanadium, tantalum or molybdenum;
the transition metal carbide is of a layered nano structure or a sheet-shaped nano structure, and when the transition metal carbide is of the layered nano structure, the number of layers is 1-5;
step three, preparing a transition metal carbide coating:
Placing the transition metal carbide prepared in the second step and the pretreated fabric fiber obtained in the first step into water, and stirring to obtain a first slurry; taking out the fabric fiber from the first slurry, and washing and drying to obtain the fabric fiber with the transition metal carbide coating;
The mass ratio of the transition metal carbide to the pretreated fabric fiber is 1:20-50; the content of the transition metal carbide in the first slurry is 1-3 mg/L;
Preparing a bismuth oxyhalide-transition metal carbide coating:
Adding the fabric fiber with the transition metal carbide coating and the Bi precursor prepared in the step three into ethylene glycol, and stirring to obtain second slurry; the Bi precursor is a salt which is soluble in glycol and contains Bi 3+; the mass ratio of the fabric fiber with the transition metal carbide coating to the Bi precursor is 1:4-8; the content of Bi precursor in the second slurry is 20-50 mg/L;
Adding halide into the second slurry, continuously stirring for 0.5-1.5 h, and adding the mass ratio of the halide to the Bi precursor is 1:4-6; taking out the fabric fiber from the second slurry, washing and drying to obtain the fabric fiber with the bismuth halide-transition metal carbide coating, wherein the fabric fiber with the bismuth halide-transition metal carbide coating has an antibacterial effect;
the halide is sodium or potassium salt of a halogen element, preferably KBr, naBr, KCl, naCl, KI or NaI.
In the above technical scheme, in the fourth step, the Bi precursor is Bi (NO 3)3·5H2O、BiCl3, bi 3+ salt soluble in ethylene glycol such as bismuth acetate, etc.).
In the technical scheme, the preparation method further comprises the step five of preparing the hydrophobic coating:
immersing the fabric fiber with the bismuth oxyhalide-transition metal carbide coating prepared in the step four into a hydrophobic organic solvent for 2-5 hours, taking out, cleaning and drying to obtain a hydrophobic antibacterial fiber;
The hydrophobic organic solvent is one or more of polydimethylsiloxane, hexadecyl trimethoxy silane and tetraethoxysilane.
In the technical scheme, the stirring speed of stirring is 500-5000 rpm.
In the technical scheme, firstly, the fabric fiber is pretreated: soaking the fabric fiber in alkaline solution with pH of 11.5-12.7 for over 2 hr, washing to eliminate residual alkali, ultrasonic washing in absolute alcohol for 30min, and drying to obtain pretreated fabric fiber.
In the technical scheme, step two, preparing transition metal carbide:
placing transition metal aluminum carbide in hydrofluoric acid solution, stirring at 30-40 ℃, washing and drying the soaked transition metal aluminum carbide, and performing ultrasonic treatment to obtain transition metal carbide;
It is a further object of the present invention to provide an antimicrobial fiber for use.
An application of the antibacterial fiber in textile technology of fabrics.
A garment made of the antibacterial fiber.
The invention has the advantages and beneficial effects that:
1. The most common sunlight is used as an external light source for fabric antibiosis, and the fabric has universality for different fabrics. The bismuth oxyhalide-transition metal carbide coating is formed on the surface of the fabric fiber at normal temperature, so that the fabric is endowed with rapid antibacterial capability on the basis of not damaging the comfort and safety of the fabric, and the antibacterial performance comprises sterilization and bacteriostasis performance.
2. The pure titanium carbide has excellent photo-thermal conversion efficiency, has poor sterilization effect under light, consumes a long time, can only generate a small amount of free radicals under sunlight, and hardly achieves the antibacterial effect. In the combination of the two, the titanium carbide improves the light absorption capacity of the composite material, so that the bismuth oxyhalide generates more electron-hole pairs, the separation of the electron-hole pairs is promoted, the utilization efficiency of photo-generated carriers is improved, and the yield of free radicals is greatly improved. The bismuth oxyhalide-transition metal carbide coating has excellent photodynamic and photothermal effects, and can achieve the effect of rapid sterilization.
3. The bismuth oxyhalide-transition metal carbide coating can generate heat and free radicals under visible light, and can achieve high-efficiency sterilization under the synergistic effect of the bismuth oxyhalide-transition metal carbide coating and the free radicals, thereby endowing the fabric with high-efficiency antibacterial function.
4. The hydrophobic coating is added on the surface of the antibacterial coating, so that the contact between titanium carbide and air is reduced, the stability of the titanium carbide is improved, the adhesion of bacteria can be inhibited, and the antibacterial capability of the coating is improved.
5. The preparation method of the bismuth oxyhalide-transition metal carbide coating-hydrophobic coating is simple, convenient and feasible, no toxic and harmful gas is generated, the method is economical and environment-friendly, the implementation difficulty is low, the equipment investment is low, the consumption resources are low, the traditional antibacterial use is made of noble metals such as silver and copper, and the technical scheme of the invention adopts materials with lower cost.
In summary, according to the technical scheme provided by the invention, sunlight is used as a light source which is necessarily contacted with the fabric fibers, and the material shows excellent sterilization performance under sunlight by constructing a coating which can respond to sunlight on the surface of the fabric fibers. The coating on the surface of the fabric fiber can form a rough nano structure on the surface, so that substances with low surface energy are modified on the surface of a rough material, and a hydrophobic coating is further formed on the surface of the material, so that the adhesion of the surface of the fabric to bacteria is reduced, and the antibacterial property of the surface of the fabric is improved.
Drawings
FIG. 1 is a view of a Scanning Electron Microscope (SEM) of the Cotton of example 1; (b) High power scanning electron microscopy of Cotton in example 1; (c) Low magnification scanning electron microscopy of Cotton-Ti 3C2 in example 1; (d) High magnification scanning electron microscopy of Cotton-Ti 3C2 in example 1; (e) a low magnification scanning electron microscope image of the Cotton-BiOBr; (f) high power scanning electron microscopy of the Cotton-BiOBr; (g) A low magnification scanning electron microscope image of Cotton-Ti 3C2 -bio-bor in example 1; (h) High power scanning electron microscope image of Cotton-Ti 3C2 -BiOBr in example 1; (i) A low magnification scanning electron microscope image of the Cotton-Ti 3C2 -bio-PDMS of example 1; (j) High magnification scanning electron microscopy of the Cotton-Ti 3C2 -BiOBr-PDMS in example 1.
FIG. 2 is a view of (a) a low-magnification scanning electron microscope of PET in example 2; (b) high power scanning electron microscope image of PET in example 2; (c) A low power scanning electron microscope image of PET-Ti 3C2 in example 2; (d) High power scanning electron microscope image of PET-Ti 3C2 in example 2; (e) a low magnification scanning electron microscope image of PET-BiOBr; (f) high magnification scanning electron microscopy of PET-BiOBr; (g) A low magnification scanning electron microscope image of PET-Ti 3C2 -bio-bor in example 2; (h) High-magnification scanning electron microscopy of PET-Ti 3C2 -BiOBr in example 2; (i) A low magnification scanning electron microscope image of PET-Ti 3C2 -bio bor-PDMS in example 2; (j) High-magnification scanning electron microscopy of PET-Ti 3C2 -BiOBr-PDMS in example 2.
FIG. 3 is a scanning electron microscope image and a surface distribution diagram of Cotton, cotton-Ti 3C2, cotton-BiOBr, and Cotton-Ti 3C2 -BiOBr in example 1.
FIG. 4 is a scanning electron microscope image and a surface profile of PET, PET-Ti 3C2, PET-BiOBr, and PET-Ti 3C2 -BiOBr in example 2.
FIG. 5 is a transmission electron microscope image of a Ti 3C2 -BiOBr coating on the surface of a fiber.
FIG. 6 is a graph showing the contact angle comparison of Cotton, cotton-Ti 3C2、Cotton-BiOBr、Cotton-Ti3C2 -BiOBr and Cotton-Ti 3C2 -BiOBr-PDMS obtained in example 1.
FIG. 7 is a graph of contact angles of PET, PET-Ti 3C2、PET-BiOBr、PET-Ti3C2 -BiOBr, and PET-Ti 3C2 -BiOBr-PDMS.
FIG. 8 is a photothermogram of Cotton, cotton-Ti 3C2、Cotton-BiOBr、Cotton-Ti3C2 -BiOBr and Cotton-Ti 3C2 -BiOBr-PDMS under simulated sunlight.
FIG. 9 is a photothermogram of PET, PET-Ti 3C2、PET-BiOBr、PET-Ti3C2 -BiOBr, and PET-Ti 3C2 -BiOBr-PDMS under simulated sunlight.
FIG. 10 is an antibacterial chart of Cotton, cotton-Ti 3C2、Cotton-BiOBr、Cotton-Ti3C2 -BiOBr and Cotton-Ti 3C2 -BiOBr-PDMS in the dark and in simulated sunlight.
FIG. 11 is an antibacterial plot of PET, PET-Ti 3C2、PET-BiOBr、PET-Ti3C2 -BiOBr and PET-Ti 3C2 -BiOBr-PDMS in the dark and simulated sunlight.
Other relevant drawings may be made by those of ordinary skill in the art from the above figures without undue burden.
Detailed Description
In order to make the person skilled in the art better understand the solution of the present invention, the following describes the solution of the present invention with reference to specific embodiments.
Example 1
Step one, pretreatment of cotton cloth:
32cm 2 of cotton cloth is placed in 100mL of 0.1mol/L sodium hydroxide solution, soaked for 2 hours, and the soaked cotton cloth is repeatedly washed in deionized water to remove residual alkali. Placing the fabric in absolute ethyl alcohol, ultrasonically cleaning for 30min, and drying to obtain experimental Cotton cloth (Cotton) for standby.
Preparing titanium carbide:
1g of titanium aluminum carbide was placed in a mixed solution of 1g of lithium fluoride and 12mol/L of 20mL of hydrochloric acid, and stirred for 24 hours under a water bath condition of 40℃at a stirring speed of 800rpm. Washing with deionized water to pH 6, adding a small amount of water, performing ultrasonic treatment at 800W for 2h, centrifuging at 3500rpm, collecting supernatant to obtain a small-layer or single-layer titanium carbide slurry, and stirring to facilitate intercalation of multiple layers of titanium carbide by lithium ions to prepare 1-5 layers of titanium carbide slurry more easily.
Step three, preparation of titanium carbide coating
The experimental Cotton cloth was placed in 3mol/L titanium carbide slurry, stirred for 1h, the Cotton cloth was taken out, unbound titanium carbide was removed by washing with water, and then the Cotton cloth was freeze-dried to obtain a titanium carbide coated Cotton fabric (Cotton-Ti 3C2).
Preparation of bismuth oxybromide/titanium carbide coating
Immersing the Cotton fabric with the titanium carbide coating in 10mL of glycol, stirring, adding 480.07mg of Bi (NO 3)3·5H2 O, stirring uniformly to disperse the Cotton fabric, stirring for 0.5h, dropwise adding 10mL of 0.1mol/L KBr into the solution, continuously stirring for 1h, taking out the Cotton cloth, cleaning and drying to obtain the Cotton fabric (Cotton-Ti 3C2 -BiOBr) with the bismuth oxybromide-titanium carbide coating.
Step five, preparation of bismuth oxybromide/titanium carbide/hydrophobic coating
Immersing the Cotton fabric with the bismuth oxybromide/titanium carbide coating in hydrophobic polydimethylsiloxane for 2 hours, taking out, cleaning and drying to obtain the Cotton fabric (Cotton-Ti 3C2 -BiOBr-PDMS) with the bismuth oxybromide/titanium carbide/polydimethylsiloxane coating.
Example two
Step one, pretreatment of terylene:
32cm 2 polyester is placed in 100mL of 0.1mol/L sodium hydroxide solution, soaked for 2 hours, and the soaked cotton cloth is repeatedly washed in deionized water to remove residual alkali. And placing the fabric in absolute ethyl alcohol, ultrasonically cleaning for 30min, and drying to obtain experimental terylene (PET) for later use.
Preparing titanium carbide:
1g of titanium aluminum carbide was placed in a mixed solution of 1g of lithium fluoride and 12mol/L of 20mL of hydrochloric acid, and stirred for 24 hours under a water bath condition of 40℃at a stirring speed of 800rpm. Washing with deionized water to pH 6, adding a small amount of water, performing ultrasonic treatment at 800W for 2h, centrifuging at 3500rpm, and collecting supernatant to obtain a small-layer or single-layer titanium carbide slurry.
Step three, preparation of titanium carbide coating
Placing experimental terylene into 3mol/L titanium carbide slurry, stirring for 1h, taking out terylene, washing to remove unbound titanium carbide, and then freeze-drying the terylene to obtain the terylene fabric (PET-Ti 3C2) with the titanium carbide coating.
Preparation of bismuth oxybromide/titanium carbide coating
Immersing the polyester fabric with the titanium carbide coating in 10mL of glycol, stirring, adding 480.07mg of Bi (NO 3)3·5H2 O, uniformly stirring to disperse the Bi, stirring for 0.5h, dropwise adding 10mL of 0.1mol/L KBr into the solution, continuously stirring for 1h, taking out cotton cloth, cleaning and drying to obtain the polyester fabric (PET-Ti 3C2 -BiOBr) with the bismuth oxybromide-titanium carbide coating.
Step five, preparation of bismuth oxybromide/titanium carbide/hydrophobic coating
Immersing the bismuth oxybromide/titanium carbide coated polyester fabric in hydrophobic polydimethylsiloxane for 2 hours, taking out, cleaning and drying to obtain the bismuth oxybromide/titanium carbide/polydimethylsiloxane coated polyester fabric (PET-Ti 3C2 -BiOBr-PDMS).
Example III
Step one, pretreatment of cotton cloth:
32cm 2 of cotton cloth is placed in 100mL of 0.1mol/L sodium hydroxide solution, soaked for 2 hours, and the soaked cotton cloth is repeatedly washed in deionized water to remove residual alkali. Placing the fabric in absolute ethyl alcohol, ultrasonically cleaning for 30min, and drying to obtain experimental Cotton cloth (Cotton) for standby.
Preparing titanium carbide:
1g of titanium aluminum carbide was placed in a mixed solution of 1g of lithium fluoride and 12mol/L of 20mL of hydrochloric acid, and stirred for 24 hours under a water bath condition of 40℃at a stirring speed of 800rpm. Washing with deionized water to pH 6, adding a small amount of water, performing ultrasonic treatment at 800W for 2h, centrifuging at 3500rpm, and collecting supernatant to obtain a small-layer or single-layer titanium carbide slurry.
Step three, preparation of titanium carbide coating
The experimental Cotton cloth was placed in 3mol/L titanium carbide slurry, stirred for 1h, the Cotton cloth was taken out, unbound titanium carbide was removed by washing with water, and then the Cotton cloth was freeze-dried to obtain a titanium carbide coated Cotton fabric (Cotton-Ti 3C2).
Preparation of bismuth oxybromide/titanium carbide coating
Immersing the Cotton fabric with the titanium carbide coating in 10mL of glycol, stirring, adding 480.07mg of Bi (NO 3)3·5H2 O, uniformly stirring to disperse the Bi, stirring for 0.5h, dropwise adding 10mL of 0.1mol/L KBr into the solution, continuously stirring for 1h, taking out the Cotton cloth, cleaning and drying to obtain the Cotton fabric with the bismuth oxybromide-titanium carbide coating (Cotton-Ti 3C2 -BiOBr).
Step five, preparation of bismuth oxybromide/titanium carbide/hydrophobic coating
Immersing the bismuth oxybromide/titanium carbide coated Cotton fabric in hydrophobic hexadecyl trimethoxy silane for 2h, taking out, cleaning and drying to obtain bismuth oxybromide/titanium carbide/hexadecyl trimethoxy silane coated Cotton fabric (Cotton-Ti 3C2 -BiOBr-HTEOS).
Example IV
Step one, pretreatment of cotton cloth:
32cm 2 of cotton cloth is placed in 100mL of 0.1mol/L sodium hydroxide solution, soaked for 2 hours, and the soaked cotton cloth is repeatedly washed in deionized water to remove residual alkali. Placing the fabric in absolute ethyl alcohol, ultrasonically cleaning for 30min, and drying to obtain experimental Cotton cloth (Cotton) for standby.
Preparing titanium carbide:
1g of titanium aluminum carbide was placed in a mixed solution of 1g of lithium fluoride and 12mol/L of 20mL of hydrochloric acid, and stirred for 24 hours under a water bath condition of 40℃at a stirring speed of 800rpm. Washing with deionized water to pH 6, adding a small amount of water, performing ultrasonic treatment at 800W for 2h, centrifuging at 3500rpm, and collecting supernatant to obtain a small-layer or single-layer titanium carbide slurry.
Step three, preparation of titanium carbide coating
The experimental Cotton cloth was placed in 3mol/L titanium carbide slurry, stirred for 1h, the Cotton cloth was taken out, unbound titanium carbide was removed by washing with water, and then the Cotton cloth was freeze-dried to obtain a titanium carbide coated Cotton fabric (Cotton-Ti 3C2).
Preparation of bismuth oxybromide/titanium carbide coating
Immersing the Cotton fabric with the titanium carbide coating in 10mL of glycol, stirring, adding 480.07mg of Bi (NO 3)3·5H2 O, uniformly stirring to disperse the Bi, stirring for 0.5h, dropwise adding 10mL of 0.1mol/L KBr into the solution, continuously stirring for 1h, taking out the Cotton cloth, cleaning and drying to obtain the Cotton fabric with the bismuth oxybromide-titanium carbide coating (Cotton-Ti 3C2 -BiOBr).
Step five, preparation of bismuth oxybromide/titanium carbide/hydrophobic coating
Immersing the bismuth oxybromide/titanium carbide coated Cotton fabric in hydrophobic tetraethoxysilane for 2 hours, taking out, cleaning and drying to obtain the bismuth oxybromide/titanium carbide/tetraethoxysilane coated Cotton fabric (Cotton-Ti 3C2 -BiOBr-TEOS).
Analysis of the detection results of examples 1 and 2:
the bismuth oxybromide coating alone was prepared as follows, and served as a control.
Preparing a bismuth oxybromide coating:
the pretreated Cotton fabric or terylene is soaked in 10mL of glycol and stirred, 480.07mg of Bi (NO 3)3·5H2 O is added and uniformly stirred to be dispersed, the mixture is stirred for 0.5h, 10mL of KBr (0.1 mol/L) is added dropwise to the solution, and the stirring is continued for 1h, the Cotton fabric or terylene is taken out, washed and dried, and the bismuth oxybromide-titanium carbide coated Cotton fabric (Cotton-BrOBi, PET-BrOBi) is obtained.
Fig. 1 shows a low-power and high-power scanning electron microscope image of a material after layer-by-layer self-assembly of a cotton fabric, which is composed of smooth fibers, as can be seen from fig. a and b. From the low-power plot (c, e, g, i) of the loaded coating, the preparation of the coating did not affect the macroscopic morphology of the fiber, indicating that the loading of the coating hardly affected the air permeability of the fiber. As can be seen from the inset of fig. 1c, ti 3C2 is in a sheet structure, which illustrates that the surface of the fiber soaked in Ti 3C2 has a lamellar structure attached, and the lamellar structure of Ti 3C2 is tightly adsorbed on the fiber of the cotton fabric (fig. 1c and 1 d). From the inset of figure f, it can be seen that the synthetic BiOBr at normal temperature is in a nano-sheet array structure, and the BiOBr nano-sheet array is attached to the surface of cotton fabric fiber. As can be seen from figures g and h, the cotton fibers carrying Ti 3C2 sheets are in the form of a nanoplatelet array. The surface of the lamellar structure of Ti 3C2 is negatively charged, so that bismuth ions can be closely adsorbed, and bromine ions are introduced, so that the nano lamellar array grows on the surface of the lamellar structure of the material in situ, and the original lamellar structure of Ti 3C2 is covered. The introduction of the hydrophobic coating did not affect the morphology change of the material (figures i and j).
Fig. 2 shows low-power and high-power scanning electron microscope images of the polyester material after layer-by-layer self-assembly, and it can be seen from the images that the surface morphology of the material is consistent with the corresponding morphology on cotton fabric, which indicates that different fabrics cannot influence the morphology of the material.
FIG. 3 shows a scanned element profile of various coatings on the surface of Cotton fabric, where it is seen that the individual cottons have only the elements C and O, and that Cotton-Ti 3C2 contains the elements Ti, C and O. The Cotton-BiOBr contains C, bi, br and O elements. Only the Cotton-Ti 3C2 -BiOBr contains Ti, C, bi, br and O elements which are uniformly distributed on the surface of the Cotton fabric fiber, which proves that Ti 3C2 and BiOBr are truly loaded on the surface of the fiber.
Fig. 4 shows the surface profile of various coatings on the polyester surface, which shows similar results as cotton fabrics.
FIG. 5 shows a transmission electron microscope image of the surface of the fiber coating Ti 3C2 -BiOBr, from which it can be seen that Ti 3C2 The (110) crystal plane of the crystal plane and the BiOBr are tightly combined together, which illustrates the existence of a Ti 3C2 and BiOBr hetero-interface.
FIG. 6 shows the contact angle of Cotton, cotton-Ti 3C2、Cotton-BiOBr、Cotton-Ti3C2 -BiOBr and Cotton-Ti 3C2 -BiOBr-PDMS in example 1. The hydrophobic property of cotton cloth and cotton cloth with different coatings is judged by measuring the contact angle, and the higher the hydrophobicity is, the stronger the bacterial adhesion resistance of the fabric is. From the figure, it can be seen that the polydimethylsiloxane leads to a significant increase in the contact angle of the fibers, improving the hydrophobic properties of the fibers.
FIG. 7 is a graph showing contact angles of PET, PET-Ti 3C2、PET-BiOBr、PET-Ti3C2 -BiOBr and PET-Ti 3C2 -BiOBr-PDMS in example 2. After the polydimethylsiloxane is modified, the surface contact angle is obviously increased, and the hydrophobicity of the material is improved.
Fig. 8 shows the photothermal curves of each cotton fiber and modified fiber in example 1 under simulated sunlight. The fiber with certain photo-thermal effect can damage bacterial protein and metabolic enzyme adhered to the surface of the fiber, and influence the activity of bacteria. Thus, different coatings were tested for photo-thermal effects under simulated sunlight. Thus, the different materials were left in water for 15min, the materials were removed, and placed under simulated sunlight for 15min. The temperature change of the material was recorded. From the graph, the temperatures of the Cotton-Ti 3C2、Cotton-Ti3C2 -BiOBr and the Cotton-Ti 3C2 -BiOBr-PDMS are rapidly increased under light, and the temperature is basically increased to 55 ℃ after 5min, which indicates that the Ti 3C2 can improve the light absorption capacity of the fiber and promote the photo-thermal conversion rate, so that the Cotton-Ti 3C2、Cotton-Ti3C2 -BiOBr and the Cotton-Ti 3C2 -BiOBr-PDMS show excellent photo-thermal effects. The Cotton-BiOBr has substantially no significant temperature change. This is because Ti 3C2 has strong light absorption under light, which can convert light into heat energy, but the absorption of bio-based on light is low, the photo-thermal conversion efficiency is low, and heat cannot be generated rapidly. Therefore, the Cotton-Ti 3C2、Cotton-Ti3C2 -BiOBr and the Cotton-Ti 3C2 -BiOBr-PDMS can generate excellent photo-thermal effect under light, and the thermal effect can aggravate the protein damage of bacteria and influence the activity of the bacteria.
Fig. 9 shows the photo-thermal profile of each polyester fiber and modified fiber in example 2 under simulated sunlight. It can also be seen that PET-Ti 3C2、PET-Ti3C2 -BiOBr and PET-Ti 3C2 -BiOBr-PDMS exhibit excellent photo-thermal effects, which result in similar photo-thermal properties to cotton fibers, which also affect the protein activity of the bacteria and reduce the survival rate of the bacteria.
FIG. 10 shows the results of bacterial plate coating of Cotton, cotton-Ti 3C2、Cotton-BiOBr、Cotton-Ti3C2 -BiOBr and Cotton-Ti 3C2 -BiOBr-PDMS under dark and light conditions. Placing 500 microliters of staphylococcus aureus bacterial liquid with the concentration of 10 7 CFU/mL into a 1mL centrifuge tube, respectively soaking a sample in the centrifuge tube for 15min, taking out cotton fibers, dividing the cotton fibers into a dark group and an illumination group, directly placing the fibers of the illumination group under simulated sunlight for irradiation for 10min, then placing the fibers into 200 microliters of liquid culture medium, ultrasonically oscillating out all bacteria on the fibers, taking a certain amount of diluted bacteria, coating the diluted bacteria on a solid agar plate, and culturing the diluted bacteria on the solid agar plate at 37 ℃ for 20 hours for counting. The dark group of fibers are directly placed in 200 microliter of liquid culture medium, all bacteria on the fibers are ultrasonically vibrated out, a certain amount of the bacteria are diluted and coated on a solid agar plate, and the fibers are used for counting after being cultured for 20 hours at 37 ℃. As can be seen from the figure, the Cotton-BiOBr showed substantially no antibacterial properties under the light conditions. The Cotton-Ti 3C2 shows a certain antibacterial property, the antibacterial rate of the Cotton-Ti 3C2 -BiOBr is 93.2%, and the Ti 3C2 -BiOBr coating has excellent antibacterial property. This is because the coating not only improves the thermal effect of the fiber under light so that the bacterial activity is reduced, but also, as a semiconductor, the BiOBr can generate photo-generated electrons and holes under simulated sunlight, wherein the photo-generated electrons can be captured by Ti 3C2 having excellent conductivity, the recombination efficiency of the photo-generated electrons and holes is reduced, and the yield of free radicals is improved. These free radicals cause peroxidation of the bacteria, which accelerates their death. Under the synergistic effect of the photo-thermal effect and the free radicals, the titanium carbide-bismuth oxybromide has excellent antibacterial effect. The antibacterial rate of the coating can reach 99.86% due to the introduction of PDMS, and the antibacterial effect of the material is greatly improved. Under dark conditions, the fibers of the Cotton-Ti 3C2, cotton-BiOBr and Cotton-Ti 3C2 -BiOBr all have no antibacterial effect, and the Cotton-Ti 3C2 -BiOBr-PDMS has a bacterial adhesion inhibition rate of 48.37%, which indicates that the hydrophobic coating can effectively inhibit bacterial adhesion. The introduction of the hydrophobic coating is proved, the adhesion of bacteria is reduced to a certain extent, the photo-thermal and free radical synergistic effect of the titanium carbide-bismuth oxybromide coating is improved, and the antibacterial rate of the fiber is improved.
FIG. 11 is an antibacterial plot of PET, PET-Ti 3C2、PET-BiOBr、PET-Ti3C2 -BiOBr and PET-Ti 3C2 -BiOBr-PDMS in the dark and simulated sunlight. The antibacterial properties of the materials were tested by the same method as cotton fibers. As can be seen from the figures, the materials exhibit similar antimicrobial properties. The antibacterial rate of the Ti 3C2 -BiOBr coating is 90.24%, which shows that the coating has obvious antibacterial effect, the antibacterial rate of the PET-Ti 3C2 -BiOBr-PDMS under the illumination condition is 98.92%, the antibacterial rate under the dark condition is 42.94%, and the Ti 3C2 -BiOBr-PDMS coating has excellent sterilization and bacteriostasis.
From the photo-thermal and antibacterial data of PET-Ti3C2-BiOBr、Cotton-Ti3C2-BiOBr、Cotton-Ti3C2-BiOBr-PDMS and PET-Ti 3C2 -BiOBr-PDMS of FIGS. 8, 9, 10 and 11, the titanium carbide-bismuth oxybromide coating has excellent photo-thermal effect, which can reduce the activity of protein in bacteria and accelerate the death of bacteria. In addition, bismuth oxybromide can generate photo-generated electrons and holes under light, titanium carbide is used as a capturing agent of the photo-generated electrons, the separation efficiency of the photo-generated electrons and the holes can be accelerated, a large number of free radicals are generated, and the free radicals can enable bacteria to generate peroxidation and accelerate the death of the bacteria. The photo-thermal and free radical synergism of the titanium carbide-bismuth oxybromide coating enables the titanium carbide-bismuth oxybromide coating to have excellent antibacterial effect. The introduction of the hydrophobic layer makes the number of bacteria adhered to the surface of the fiber less, and improves the antibacterial rate of the fiber under the action of the same titanium carbide-bismuth oxybromide coating.
Bismuth oxyhalide bisx (x=cl, br, I) has an irregular crystal structure and indirect electronic transitions. The nature of the indirect transition means that the excited electrons need to travel a spatial distance to be emitted to the valence band, which reduces the recombination efficiency of the photogenerated electron holes. Bismuth oxyhalides have the same characteristic, and as the atomic number increases, the forbidden bandwidth of the semiconductor gradually decreases, which increases the photocatalytic activity under light. Bismuth oxychloride thus also exhibits excellent photocatalytic effects. Thus, bismuth oxybromide in embodiments may be extended to bismuth oxychloride as well as bismuth oxyiodide. Under sunlight, bismuth oxychloride and bismuth oxyiodide can be excited to generate photo-generated electrons, and titanium carbide with excellent conductivity can rapidly capture the photo-generated electrons, so that a large amount of photo-generated electrons can generate free radicals, and bacteria are damaged.
In addition, titanium carbide is one of transition metal carbides, which has similar characteristics to the transition metal carbides. As a novel two-dimensional material, the transition metal carbide (niobium carbide, vanadium carbide, molybdenum carbide and tantalum carbide) has complete metal atomic layers and rich surface functional groups, and combines the metal conductivity of the transition metal carbide and the hydrophilicity of the hydroxyl/oxygen/fluorine end group surface of the transition metal carbide. Therefore, the transition metal carbide can be used as a trap for capturing electrons, so that the photo-generated electrons of the semiconductor are quickly transferred, the recombination of the photo-generated electrons and holes is inhibited, and the utilization rate of the electrons is improved. Thus, the titanium carbide in the examples may be replaced with other transition metal carbides (niobium carbide, vanadium carbide, molybdenum carbide, tantalum carbide).
Moreover, relational terms such as "first" and "second", and the like, may be used solely to distinguish one element from another element having the same name, without necessarily requiring or implying any actual such relationship or order between such elements.
The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.
Claims (8)
1. The antibacterial fiber is characterized by comprising a textile fiber, an antibacterial coating coated on the outer surface of the textile fiber and a hydrophobic layer coated outside the antibacterial coating, wherein the antibacterial coating comprises transition metal carbide and bismuth oxyhalide; the transition metal carbide is in a layered nano structure or a sheet nano structure, and bismuth oxyhalide is distributed on the surface of the transition metal carbide in a nano sheet array form; bismuth ions in the bismuth oxyhalide and the transition metal carbide are adsorbed and combined through electrostatic force, and a heterogeneous interface is formed between the bismuth oxyhalide and the transition metal carbide; the load capacity of the transition metal carbide nano-sheet on the fiber is 0.5-1.5 mg/cm 2, and the load capacity of the bismuth oxyhalide on the fiber is 0.5-1.5 mg/cm 2;
the fabric fiber is made of one or more of cotton, terylene, chinlon, spandex, acrylon or silk;
the transition metal carbide is titanium carbide;
The bismuth oxyhalide is bismuth oxybromide;
The hydrophobic layer is formed by one or more of polydimethylsiloxane, hexadecyl trimethoxy silane or tetraethoxysilane, and the thickness is 10-80 nm.
2. The antibacterial fiber according to claim 1, wherein when the transition metal carbide is in a layered nano structure, the number of layers is 1 to 5.
3. The antimicrobial fiber according to claim 1, wherein the transition metal carbide has a size of 1 to 5 μm; the size of the bismuth oxyhalide is 300-800 nm.
4. A method for preparing an antibacterial fiber, comprising the following steps:
step one, pretreatment of fabric fibers:
placing the fabric fibers in an alkaline solution with the pH value of 11-13, soaking for more than 2 hours, washing the soaked fabric fibers to remove residual alkali, and drying to obtain pretreated fabric fibers;
the fabric fiber is made of one or more of cotton, terylene, chinlon, spandex, acrylon or silk;
Step two, preparing transition metal carbide:
Placing transition metal aluminum carbide in hydrofluoric acid solution, stirring at 30-40 ℃, washing and drying the soaked transition metal aluminum carbide to obtain transition metal carbide;
The concentration of the hydrofluoric acid solution is 20-40wt% and the concentration of lithium ions is 30-50 mg/mL;
The transition metal is one or more of titanium, niobium, vanadium, tantalum or molybdenum;
the transition metal carbide is of a layered nano structure or a sheet-shaped nano structure, and when the transition metal carbide is of the layered nano structure, the number of layers is 1-5;
step three, preparing a transition metal carbide coating:
Placing the transition metal carbide prepared in the second step and the pretreated fabric fiber obtained in the first step into water, and stirring to obtain a first slurry; taking out the fabric fiber from the first slurry, and washing and drying to obtain the fabric fiber with the transition metal carbide coating;
The mass ratio of the transition metal carbide to the pretreated fabric fiber is 1:20-50; the content of the transition metal carbide in the first slurry is 1-3 mg/L;
Preparing a bismuth oxyhalide-transition metal carbide coating:
adding the fabric fiber with the transition metal carbide coating and the Bi precursor prepared in the step three into ethylene glycol, and stirring to obtain second slurry; the Bi precursor is a salt which is soluble in glycol and contains Bi 3+; the mass ratio of the fabric fiber with the transition metal carbide coating to the Bi precursor is 1:4-8; the content of the Bi precursor in the second slurry is 20-50 mg/L;
Adding halide into the second slurry, continuously stirring for 0.5-1.5 h, and adding the halide and the Bi precursor in a mass ratio of 1:4-6; taking out the fabric fiber from the second slurry, washing and drying to obtain the fabric fiber with the bismuth halide-transition metal carbide coating, wherein the fabric fiber with the bismuth halide-transition metal carbide coating has an antibacterial effect;
the halide is KBr or NaBr;
The preparation method further comprises the step five of preparing the hydrophobic coating:
Immersing the fabric fiber with the bismuth oxyhalide-transition metal carbide coating prepared in the step four into a hydrophobic organic solvent for 2-5 hours, taking out, cleaning and drying to obtain a hydrophobic antibacterial fiber;
The hydrophobic organic solvent is one or more of polydimethylsiloxane, hexadecyl trimethoxy silane and tetraethoxysilane.
5. The method for producing an antibacterial fiber according to claim 4, wherein,
Step one, pretreatment of fabric fibers: soaking the fabric fiber in alkaline solution with pH of 11.5-12.7 for over 2 hr, washing to eliminate residual alkali, ultrasonic washing in absolute alcohol for 30min, and drying to obtain pretreated fabric fiber.
6. The method for producing an antibacterial fiber according to claim 4, wherein,
Step two, preparing transition metal carbide:
placing transition metal aluminum carbide in hydrofluoric acid solution, stirring at 30-40 ℃, washing and drying the soaked transition metal aluminum carbide, and performing ultrasonic treatment to obtain transition metal carbide;
The Bi precursor is Bi (one or more of NO 3)3·5H2O、BiCl3 or bismuth acetate;
the stirring speed of stirring is 500-5000 rpm.
7. Use of the antimicrobial fiber according to claim 1 in a textile process of a fabric.
8. A garment made from the antimicrobial fiber of claim 1.
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