CN112156776A - Porous ceramic load Ag/TiO2Preparation method of (1) - Google Patents
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- 239000000919 ceramic Substances 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 27
- 229910021649 silver-doped titanium dioxide Inorganic materials 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002791 soaking Methods 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 150000003608 titanium Chemical class 0.000 claims abstract description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000008103 glucose Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 238000007605 air drying Methods 0.000 claims description 3
- 150000007514 bases Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 14
- 239000002105 nanoparticle Substances 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 239000000843 powder Substances 0.000 abstract description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
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- 230000003385 bacteriostatic effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 210000000170 cell membrane Anatomy 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
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- 102000004190 Enzymes Human genes 0.000 description 1
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- 239000005909 Kieselgur Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 108010073357 cyanoginosin LR Proteins 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- ZYZCGGRZINLQBL-GWRQVWKTSA-N microcystin-LR Chemical compound C([C@H](OC)[C@@H](C)\C=C(/C)\C=C\[C@H]1[C@@H](C(=O)N[C@H](CCC(=O)N(C)C(=C)C(=O)N[C@H](C)C(=O)N[C@@H](CC(C)C)C(=O)N[C@H]([C@H](C)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N1)C(O)=O)C(O)=O)C)C1=CC=CC=C1 ZYZCGGRZINLQBL-GWRQVWKTSA-N 0.000 description 1
- DIDLWIPCWUSYPF-UHFFFAOYSA-N microcystin-LR Natural products COC(Cc1ccccc1)C(C)C=C(/C)C=CC2NC(=O)C(NC(CCCNC(=N)N)C(=O)O)NC(=O)C(C)C(NC(=O)C(NC(CC(C)C)C(=O)O)NC(=O)C(C)NC(=O)C(=C)N(C)C(=O)CCC(NC(=O)C2C)C(=O)O)C(=O)O DIDLWIPCWUSYPF-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
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- 230000000241 respiratory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
- A61L2/08—Radiation
- A61L2/088—Radiation using a photocatalyst or photosensitiser
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
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Abstract
The invention discloses a porous ceramic load Ag/TiO2The preparation method comprises the following specific steps: putting the porous ceramic into a mixed solution of an alkaline compound, water, ethanol and acetone, performing ultrasonic treatment, washing and drying; taking out, soaking in a soluble titanium salt solution, and drying; stirring tetrabutyl titanate solution and concentrated hydrochloric acid solution, and mixing with porous ceramicTransferring to a hydrothermal reaction kettle, finishing the hydrothermal reaction, washing and drying the porous ceramic supported TiO2(ii) a Soaking the porous ceramic in a mixed solution of silver nitrate and glucose, drying, and performing ultraviolet irradiation to obtain the porous ceramic supported Ag/TiO2. The invention effectively improves the Ag/TiO content2The photocatalytic antibacterial effect and the powder utilization rate of the nano particles.
Description
Technical Field
The invention relates to material science and nano material technology, in particular to porous ceramic supported Ag/TiO2The preparation method of (1).
Background
TiO has long been used2Has been attracting attention as a conventional photocatalytic material. Under UV irradiation, TiO2When the valence electron moves to the conduction band, an excited electron and a hole are generated, and the hole is absorbed by water or hydroxyl to generate a hydroxyl radical, so that the TiO2Has remarkable photocatalytic activity and potential application prospect in the purification treatment of water and air. On the other hand, titanium dioxide has a wide band gap, Ag and TiO2When combined, can reduce TiO2Prevents the rapid recombination of electron-hole pairs under the irradiation of ultraviolet rays, thereby improving the photocatalytic activity under the irradiation of visible light.
Ag+Binding to bacterial cell membranes can cause damage to bacterial cell membranes and can also destroy the DNA structure of bacteria, thereby killing the bacteria. At the same time, Ag+Interaction with sulfhydryl groups in proteins also leads to inactivation of respiratory enzymes. Further, Ag acts on TiO due to the synergistic effect of nano-silver2Has a great enhancing effect on the antibacterial activity of the compound. Thus, Ag/TiO2The nano composite material can effectively kill bacteria and viruses.
However, during use, Ag and TiO2The nano particles are easy to agglomerate, so that the photocatalytic efficiency of the product is reduced; meanwhile, the particles are difficult to recover, so that material waste and environmental pollution are easily caused, and the problems bring certain difficulties to practical application. To make Ag and TiO2The nano particles are uniformly dispersed and are used by scientific research personnelThey are supported on activated carbon, porous silica gel, diatomaceous earth, etc. For example, Chenjunwei and the like adopt a sol-gel method to prepare a diatomite-loaded nitrogen-doped titanium dioxide modified nano material, and carry out photocatalytic treatment on microcystin LR, wherein the degradation rate can reach 95.0% after 6 hours of reaction. Although the supported method solves the problem of low photocatalytic efficiency to some extent, the problem of difficulty in recovering the powder is still not solved. The porous ceramic contains uniform three-dimensional holes, has high porosity and uniform pore distribution, has rough surface and larger specific surface area, and is loaded with TiO2The ideal carrier of (2).
Therefore, in combination with the above problems, there is provided a porous ceramic supported Ag/TiO2The preparation method of (2) is a problem which needs to be solved by the technical personnel in the field.
Disclosure of Invention
In view of the above, the invention provides a porous ceramic supported Ag/TiO2The invention is to mix Ag and TiO2The nano particles are loaded on the porous ceramic with large specific surface area, low density and high porosity, thereby effectively improving the Ag/TiO2The photocatalytic antibacterial effect and the powder utilization rate of the nano particles.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
porous ceramic load Ag/TiO2The preparation method comprises the following specific steps:
s1, putting the porous ceramic into a mixed solution of an alkaline compound, water, ethanol and acetone, carrying out ultrasonic treatment for 30min, taking out the porous ceramic, washing the porous ceramic with deionized water, and drying the porous ceramic at the temperature of 50-60 ℃;
s2, dissolving soluble titanium salt in an ice water mixture, preparing a solution with the concentration of 0.05-0.5mol/L, adding the porous ceramic treated in the step S1, soaking for 10-15min, taking out the porous ceramic, placing the porous ceramic in an oven, drying at the constant temperature of 70-80 ℃ for 30-40min, and repeating the soaking and drying processes again;
s3, under magnetic stirring, adding deionized water into tetrabutyl titanate solution, then dropwise adding concentrated hydrochloric acid solution, magnetically stirring for 30-60min, placing the mixed solution into a stainless steel hydrothermal reaction kettle, immersing the porous ceramic treated in the step S2 into the mixed solution of the hydrothermal reaction kettle, heating for hydrothermal reaction, placing the stainless steel reaction kettle into a constant-temperature oven, preserving heat for 12-24h, and naturally cooling to room temperature;
s4, taking out the porous ceramic treated in the step S3, washing the porous ceramic for 3-4 times by using ethanol and deionized water respectively, putting the porous ceramic into a forced air drying oven, setting the temperature to be 50-100 ℃, and drying the porous ceramic at constant temperature for 12-24 hours to obtain the porous ceramic supported TiO2；
S5, loading the porous ceramic obtained in the step S4 with TiO2Soaking in mixed solution of silver nitrate and glucose for 12-24 hr, taking out, drying in drying oven for 50-80min, soaking for 10-60min, drying for 50-80min, repeating soaking and drying for 2-4 times, and irradiating with 500W ultraviolet lamp for 0.5-2 hr to obtain porous ceramic supported Ag/TiO2。
Preferably, the alkaline compound in step S1 is one of NaOH and KOH.
Preferably, the volume ratio of the basic compound, the water, the ethanol and the acetone in the step S1 is 1:1:1: 1.
Preferably, the acetone in step S1 may be replaced by acetylacetone.
Preferably, the soluble titanium salt in step S2 is one of titanium tetrachloride and titanyl sulfate.
Preferably, the volume ratio of the deionized water to the tetrabutyl titanate solution to the concentrated hydrochloric acid solution in the step S3 is 30:1: 30-90.
Preferably, the temperature of the temperature-rising hydrothermal reaction in the step S3 is set to 160-220 ℃.
Preferably, the temperature increase rate in step S3 is 50 ℃/h.
Preferably, the heat preservation time in the step S3 is 16-24 h.
Preferably, the concentration of the silver nitrate solution in the step S5 is 30-100mmol/L, and the concentration of the glucose solution is 0.6-1.4 mol/L.
Preferably, the drying temperature in the step S5 is 80 to 110 ℃.
By adopting the technical scheme, the invention has the following beneficial effects:
(1) the invention firstly adopts the dipping method to grow the seed layer on the porous ceramics. The seed layer can reduce porous ceramic and TiO2Lattice mismatch between nanoparticles to enhance TiO2The crystallinity of the nano-particles is beneficial to the subsequent synthesis of TiO2Nanoparticles are grown on the seed layer. Secondly, hydrothermal method is adopted to prepare the titanium dioxide2Continued TiO growth on the seed layer2The product has the advantages of fine (nanometer) powder, high purity, good dispersibility, uniformity, narrow distribution, no agglomeration, good crystal form, controllable shape, etc.
(2) The porous ceramic adopted by the invention is blocky and has controllable size. In addition, the porous ceramic prepared by the invention can be loaded with Ag/TiO2The material is placed in a net-shaped woven bag, so that the Ag/TiO loaded porous ceramic can be regulated and controlled2The amount of material is sufficient for different practical applications.
(3) The porous ceramic has the advantages of low price, easy acquisition, large specific surface area, high mechanical strength, good adsorption performance, no pollution to the environment, good compatibility with a catalyst and the like, so the invention selects the inorganic porous ceramic as a carrier, and Ag/TiO is loaded on the inorganic porous ceramic2Nano-particles, and preparing the photocatalytic antibacterial material. Ag/TiO22The porous ceramic is firmly combined with the porous ceramic and is not easy to fall off, the agglomeration of the catalyst is avoided, the recycling is realized, bacteria can be adsorbed to the surface of the carrier by utilizing the good adsorption performance of the porous ceramic, and the Ag/TiO is enlarged2The contact probability with bacteria is improved, and the Ag/TiO is improved2The degradation efficiency of (a). The photocatalytic antibacterial material prepared by the invention has 99.96% of sterilization effect on escherichia coli, and can be recycled.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required in the description of the embodiments are briefly introduced below, the drawings in the description below are merely the embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a photograph of a porous ceramic according to example 1 of the present invention;
FIG. 2 is a SEM photograph of a porous ceramic according to example 1 of the present invention;
FIG. 3 shows Ag/TiO Supported porous ceramics according to example 1 of the present invention2A photo;
FIG. 4 shows Ag/TiO Supported porous ceramics according to example 1 of the present invention2Electron microscope photographs;
FIG. 5 is an XRD pattern of the porous ceramic supported Ag/TiO2 of example 1 of the present invention;
FIG. 6 is an infrared spectrum of Ag/TiO2 supported on a porous ceramic according to example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment 1 of the invention discloses porous ceramic supported Ag/TiO2The preparation method adopts the following technical scheme:
(1) preparation of porous ceramic-supported TiO2
The appearance of the porous ceramic used in this example 1 is shown in FIG. 1, and its electron scanning electron micrograph is shown in FIG. 2. Putting the porous ceramic into a mixed solution of 0.5% NaOH, water, ethanol and acetone in a volume ratio of 1:1:1:1, performing ultrasonic treatment for 30min, then cleaning with deionized water, and drying at 60 ℃; 2mL of 0.1mmoL TiCl4Adding the solution into 180ml of ice water mixture, then soaking the cleaned porous ceramic in the solution for 10min, drying in a drying oven at constant temperature of 80 ℃ for 30min, then soaking again for 10min, and drying for 30 min; wherein the volume ratio of the deionized water to the tetrabutyl titanate solution to the concentrated hydrochloric acid solution is 30:1: 30-90.
Under the condition of magnetic stirring, 0.5mL of tetrabutyl titanate solution is added into 15mL of deionized water, 15mL of concentrated hydrochloric acid solution is added dropwise,magnetically stirring for 30min, putting the mixed solution into a 50mL stainless steel hydrothermal reaction kettle, immersing the porous ceramic into the mixed solution of the stainless steel hydrothermal reaction kettle, putting the stainless steel hydrothermal reaction kettle into a constant-temperature oven, heating to 160 ℃, reacting for 16h, and cooling to room temperature; taking out porous ceramic loaded TiO2Respectively washing with ethanol and deionized water for 3 times, placing into a forced air drying oven at 50 deg.C, drying at constant temperature for 12 hr to obtain porous ceramic supported TiO2。
(2) Preparation of porous ceramic supported Ag/TiO2
Preparing a mixed solution of 0.8mol/L glucose and 50mmol/L silver nitrate, and loading the prepared porous ceramic with TiO2Soaking the mixed solution for 12h, drying in a drying oven for 80min, soaking for 60min again, drying for 80min, repeating soaking and drying processes for 3 times, and irradiating with 500W ultraviolet lamp for 1h to obtain porous ceramic supported Ag/TiO2。
Porous ceramic supported Ag/TiO2The appearance of the sample is shown in fig. 3. As can be seen from the figure, a layer of white substance is attached on the porous ceramic, and the combination is relatively firm. FIG. 4 shows porous ceramic supported Ag/TiO2The scanning electron microscope photo of the sample shows that rod-shaped TiO is uniformly distributed on the surface and in the pore channels of the porous ceramic2And Ag nanoparticles.
(3) Porous ceramic supported Ag/TiO2Photocatalytic antibacterial experiment
Comparative example TiO-Supported ordinary Zeolite from Shenyang Ltd2The antibacterial material was used as a control example. Determination of porous ceramic load Ag/TiO2The results of the test for the antibacterial activity against Staphylococcus aureus are shown in Table 1. And (3) carrying out bacteriostatic performance detection on escherichia coli and staphylococcus aureus bacteriostatic rate according to the specification of JC/T897-2002.
The porous ceramic supported Ag/TiO shown in FIG. 52The XRD pattern of (A) shows that the sample is made of SiO2、TiO2Combined with Ag, confirmed that Ag and TiO2Successfully loaded on the porous ceramic.
According to the infrared spectrogram of the porous ceramic supported Ag/TiO2 shown in FIG. 6，Ag/TiO2The particles are 3416, 1635, 1384, 663 and 606cm-1Where shows a characteristic signal of 3416cm-1The broad band of sites can be attributed to hydroxyl group aggregation and extensive vibration of interlayer water molecules. 1635cm-1The peak at (b) is derived from the vibration of the O-H bond of water, 1384cm-1The peak at (A) can be attributed to the Ag-O-Ti bond. 1000cm-1The following vibration peaks originated from Ti-O-Ti bonds of 663 cm and 606cm-1The peak at (a) is the anatase peak of TiO 2. 1135-1194cm-1The vibration peak at the position is attributed to the Si-O bond and the stretching vibration peak of the Si-O-Si bond, wherein 1100cm-1The peak at (A) belongs to the asymmetric stretching vibration of the Si-O-Si bond. 800 and 471cm-1The peak is the symmetric stretching vibration peak and the bending vibration peak of the Si-O-Si bond. Based on the above analysis, Ag/TiO can be known2The particles are attached to the porous ceramic, and the Ag/TiO is successfully synthesized by the invention2A porous ceramic material.
Example 2
The concentration of the silver nitrate solution used was 60mmol/L, the other operation steps were the same as in example 1, and the results of the antibacterial test obtained are shown in Table 1.
Example 3
TiCl4The solution was added in an amount of 4mmol, and other procedures were the same as in example 1, and the results of the antibacterial test obtained are shown in Table 1.
Example 4
The hydrothermal reaction temperature was 220 deg.C, the other operation steps were the same as in example 1, and the results of the antibacterial test obtained are shown in Table 1.
Example 5
The titanium salt solution used was titanyl sulfate, the other operation steps were the same as in example 1, and the results of the antibacterial test obtained are shown in table 1.
TABLE 1
As can be seen from the data of the results of the tests of the antibacterial properties of examples 1 to 5 in Table 1, the porous ceramics prepared according to the present invention supported Ag/TiO2Whether or notHas excellent antibacterial performance under ultraviolet irradiation.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. Porous ceramic load Ag/TiO2The preparation method is characterized by comprising the following specific steps:
s1, putting the porous ceramic into a mixed solution of an alkaline compound, water, ethanol and acetone, carrying out ultrasonic treatment for 30min, taking out the porous ceramic, washing the porous ceramic with deionized water, and drying the porous ceramic at the temperature of 50-60 ℃;
s2, dissolving soluble titanium salt in an ice water mixture, preparing a solution with the concentration of 0.05-0.5mol/L, adding the porous ceramic treated in the step S1, soaking for 10-15min, taking out the porous ceramic, placing the porous ceramic in an oven, drying at the constant temperature of 70-80 ℃ for 30-40min, and repeating the soaking and drying processes again;
s3, under magnetic stirring, adding deionized water into tetrabutyl titanate solution, then dropwise adding concentrated hydrochloric acid solution, magnetically stirring for 30-60min, placing the mixed solution into a stainless steel hydrothermal reaction kettle, immersing the porous ceramic treated in the step S2 into the mixed solution of the hydrothermal reaction kettle, heating for hydrothermal reaction, placing the stainless steel reaction kettle into a constant-temperature oven, preserving heat for 12-24h, and naturally cooling to room temperature;
s4, taking out the porous ceramic treated in the step S3, washing the porous ceramic for 3-4 times by using ethanol and deionized water respectively, putting the porous ceramic into a forced air drying oven, setting the temperature to be 50-100 ℃, and drying the porous ceramic at constant temperature for 12-24 hours to obtain the porous ceramic supported TiO2；
S5, loading the porous ceramic obtained in the step S4 with TiO2Soaking in mixed solution of silver nitrate and glucoseSoaking in the solution for 12-24 hr, taking out, drying in drying oven for 50-80min, soaking for 10-60min, drying for 50-80min, repeating soaking and drying for 2-4 times, and irradiating with 500W ultraviolet lamp for 0.5-2 hr to obtain porous ceramic supported Ag/TiO2。
2. The porous ceramic supported Ag/TiO of claim 12The preparation method of (5), wherein the basic compound in step S1 is one of NaOH and KOH.
3. The porous ceramic supported Ag/TiO of claim 12The method of (5) is characterized in that the volume ratio of the basic compound, water, ethanol and acetone in step S1 is 1:1:1: 1.
4. The porous ceramic supported Ag/TiO of claim 12The method of (5) is characterized in that the soluble titanium salt in step S2 is one of titanium tetrachloride and titanyl sulfate.
5. The porous ceramic supported Ag/TiO of claim 12The preparation method is characterized in that the volume ratio of the deionized water to the tetrabutyl titanate solution to the concentrated hydrochloric acid solution in the step S3 is 30:1: 30-90.
6. The porous ceramic supported Ag/TiO of claim 12The preparation method is characterized in that the temperature of the temperature-rising hydrothermal reaction in the step S3 is set to be 160-220 ℃, and the heat preservation time is 16-24 h.
7. The porous ceramic supported Ag/TiO of claim 12The preparation method of (5) is characterized in that the concentration of the silver nitrate solution in the step S5 is 30-100mmol/L, and the concentration of the glucose solution is 0.6-1.4 mol/L.
8. The porous ceramic supported Ag/TiO of claim 12The method of (5), wherein the drying temperature in the step S5 is 80 to 110 ℃.
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