CN113952952A - Ag2Mo2O7/TiO2Antibacterial material and preparation method and application thereof - Google Patents
Ag2Mo2O7/TiO2Antibacterial material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 85
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 23
- 230000003385 bacteriostatic effect Effects 0.000 claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims abstract description 13
- 241000588724 Escherichia coli Species 0.000 claims abstract description 12
- 239000002127 nanobelt Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 230000002779 inactivation Effects 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000002074 nanoribbon Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000009849 deactivation Effects 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 244000052769 pathogen Species 0.000 abstract description 2
- 230000001717 pathogenic effect Effects 0.000 abstract description 2
- 229910001316 Ag alloy Inorganic materials 0.000 abstract 1
- 239000000956 alloy Substances 0.000 abstract 1
- 239000002114 nanocomposite Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 6
- 238000004659 sterilization and disinfection Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000010956 nickel silver Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- MHLYOTJKDAAHGI-UHFFFAOYSA-N silver molybdate Chemical compound [Ag+].[Ag+].[O-][Mo]([O-])(=O)=O MHLYOTJKDAAHGI-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/686—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with molybdenum
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/23—
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention discloses Ag2Mo2O7/TiO2An antibacterial material and a preparation method and application thereof, belonging to the technical field of nano composite antibacterial materials. Technique of the inventionThe key points of the scheme are as follows: with surface-roughened TiO2The nano-belt is used as a matrix and passes through the narrow band gap Ag2Mo2O7Semiconductor composition to prepare a new heterojunction Ag2Mo2O7/TiO2Bacteriostatic material, this bacteriostatic material can be used for the deactivation escherichia coli of photocatalysis. The formation of the heterojunction not only accelerates the separation of the photoproduction electrons and the holes, but also effectively inhibits Ag2Mo2O7The photo-corrosion of the Ag-alloy material is prepared by improving method2Mo2O7/TiO2The antibacterial material is expected to be popularized and applied in pathogen inactivation as an effective antibacterial material.
Description
Technical Field
The invention belongs to the technical field of nano antibacterial composite materials, and particularly relates to Ag2Mo2O7/TiO2Antibacterial material and its preparation method and application.
Background
Of the numerous semiconductor photocatalytic materials, titanium dioxide (TiO)2) Because of the advantages of no toxicity, low price, high stability, strong oxidation-reduction property and the like, the photocatalyst is widely applied to the field of photocatalytic sterilization. But TiO 22The forbidden band width is large (3.2 eV), only ultraviolet light can be absorbed, and the quantum yield is low, so that the practical application of the quantum dot quantum. The composite material can improve the absorption capacity of the material to visible light and promote the effective separation of the broad-spectrum charge by compounding the material with a narrow-band semiconductor, thereby improving TiO2One of the effective ways of photocatalytic activity.
Silver-based semiconductors have attracted extensive attention due to their characteristics of strong light absorption, high quantum yield, good photocatalytic activity, and the like. Ag+Has a 4d 10And an electron orbit which can participate in band construction of the semiconductor, narrows a band gap of the silver-based semiconductor, and exhibits visible light responsiveness. At the same time, due to the photogeneration of silver-based semiconductorsThe effective mass of the holes and electrons is small, which is beneficial to the rapid migration of photo-generated charges. Therefore, the silver-based semiconductor has good visible light response performance and higher photoproduction charge migration rate, and is widely applied to the field of photocatalysis disinfection and sterilization. Adding TiO into the mixture2Combines with the advantages of silver series semiconductor, not only can expand TiO2The light absorption range of visible light is widened, the utilization rate of the visible light is improved, the separation of photoproduction electrons and holes can be promoted, and the photocatalytic bacteriostatic activity of the material is improved.
Silver molybdate (Ag)2Mo2O7) Is a new silver semiconductor photocatalysis material, the valence band top of the material is formed by the hybridization of Ag 4d and O2 p orbitals, and the existence of the hybrid orbitals reduces Ag2Mo2O7The band gap energy of (1). Ag2Mo2O7The band gap energy of monoclinic system and triclinic system is 2.98eV and 2.65eV respectively, both can absorb visible light, and the chemical activity of the monoclinic system and triclinic system is high, so that the monoclinic system and the triclinic system are frequently applied to the field of wastewater purification recently. In addition, Ag2Mo2O7Has broad-spectrum antibacterial property as a novel inorganic antibacterial agent, and is attracting much attention. But Ag2Mo2O7Has the disadvantages of narrow light absorption range and easy occurrence of photo-corrosion to generate simple Ag substance which may occupy Ag2Mo2O7Thereby reducing Ag2Mo2O7Photocatalytic activity of (1).
Disclosure of Invention
In order to solve the technical problems, the invention provides Ag2Mo2O7/TiO2Bacteriostatic material and preparation method thereof, wherein the method uses TiO with roughened surface2The nano-belt is used as a matrix and passes through the narrow band gap Ag2Mo2O7Semiconductor composition to prepare a new heterojunction Ag2Mo2O7/TiO2Bacteriostatic material, this bacteriostatic material can be used for the deactivation escherichia coli of photocatalysis.
The invention adopts the following technical scheme to solve the technical problems2Mo2O7/TiO2The preparation method of the antibacterial material is characterized by comprising the following specific steps:
step S1: dispersing P25 into a NaOH solution, carrying out hydrothermal reaction at 180 ℃ for 48h, cooling to room temperature, washing with deionized water to neutrality, dispersing in a hydrochloric acid solution, stirring for 24h, adding the material treated by the hydrochloric acid solution into a strong acid solution, stirring, and carrying out hydrothermal reaction at 100 DEG CoC, reacting for 12 hours, washing to be neutral by water, and reacting at 70 DEGoC, drying, heating to 500 ℃ at a heating rate of 5 ℃/min in a muffle furnace, calcining for 2h, and naturally cooling to room temperature to obtain a white product, namely the rough-surface TiO2A nanoribbon;
step S2: TiO obtained in step S12Dispersing the nanobelts into an ammonium molybdate solution, stirring, adding a silver nitrate solution, adjusting the pH value of a mixed system to 6, continuously stirring for 2 hours, transferring the obtained suspension into a reaction kettle, reacting for 12 hours at 150 ℃, cooling to room temperature, centrifuging, washing and drying to obtain Ag2Mo2O7/TiO2And (3) a bacteriostatic material.
As a further improvement of the invention, the concentration of the hydrochloric acid solution in the step S1 is 0.1M.
As a further improvement of the invention, the strong acid solution in step S1 is a 0.02M sulfuric acid solution.
The invention also provides Ag prepared by the preparation method2Mo2O7/TiO2Bacteriostatic material which makes full use of TiO2And Ag2Mo2O7Has the advantages of excellent synergistic antibacterial effect, and simultaneously, because of TiO2And Ag2Mo2O7A heterojunction is formed between the two, the separation of the widely generated electron-hole pairs is promoted, and Ag is greatly inhibited2Mo2O7The stability of the heterojunction material is improved. Thus, Ag2Mo2O7/TiO2The antibacterial material is expected to be popularized and applied in pathogen inactivation as an effective antibacterial material.
As a further improvement of the invention, the Ag is2Mo2O7/TiO2The antibacterial material is applied to photocatalytic inactivation of escherichia coli.
The invention has the following advantages and beneficial effects: ag prepared by the invention2Mo2O7/TiO2TiO in bacteriostatic material2The surface of the nanobelt is composed of particles having a size of about 20nm, and the rough surface enhances TiO2Provides more active sites for the reaction. Simultaneously, preparing Ag2Mo2O7/TiO2In the process of antibacterial material, TiO with roughened surface2The nanobelts provide more nucleation centers for the reaction, so that the Ag+Is uniformly distributed in TiO2Surface of, lead to Ag2Mo2O7Uniformly and tightly growing on TiO in the form of nano particles2Forming Ag on the surface of the nanobelt2Mo2O7/TiO2A heterojunction. The formation of the heterojunction not only accelerates the separation of the photoproduction electrons and the holes, but also effectively inhibits Ag2Mo2O7The photo-corrosion improves the photo-catalytic activity and stability of the heterojunction.
Drawings
FIG. 1 shows TiO prepared in accordance with an example of the present invention2、Ag2Mo2O7And Ag2Mo2O7/TiO2FESEM image of (B);
FIG. 2 shows TiO prepared in accordance with an example of the present invention2、Ag2Mo2O7And Ag2Mo2O7/TiO2An XPS map of (A);
FIG. 3 shows TiO prepared in accordance with an embodiment of the present invention2、Ag2Mo2O7And Ag2Mo2O7/TiO2An XRD pattern of (a);
FIG. 4 shows TiO prepared in accordance with an embodiment of the present invention2、Ag2Mo2O7And Ag2Mo2O7/TiO2Ultraviolet-visible diffuse reflectance spectrogram of (1);
FIG. 5 shows TiO prepared in accordance with an example of the present invention2、Ag2Mo2O7And Ag2Mo2O7/TiO2Photocurrent and EIS plots of;
FIG. 6 shows TiO prepared in accordance with an embodiment of the present invention2、Ag2Mo2O7And Ag2Mo2O7/TiO2(40. mu.g/mL) against E.coli (1.6X 10)7cfu/mL) inactivation effect: (a) dark conditions, (b) light conditions;
FIG. 7 shows Ag obtained in accordance with an example of the present invention2Mo2O7/TiO2FESEM image of (40. mu.g/mL) treated E.coli: (a) 0min, (b) 5min, (c) 15min, (d) 30min, (e) 45min, and (f) 60 min.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Examples
Ag2Mo2O7/TiO2Preparing a bacteriostatic material:
0.8g P25 was dispersed into 80mL of NaOH solution (10M), stirred for 1h, then transferred to a 100mL reaction kettle, kept at 180 ℃ for 48h, cooled to room temperature, washed to neutrality with deionized water, dispersed into hydrochloric acid solution (0.1M), and stirred continuously for 24 h. The material was then transferred to 80mL of H2SO4Stirring the solution (0.02M) and transferring the above materials to a reaction kettle at 100 deg.CoKeeping the temperature for 12h, washing the mixture to be neutral by deionized water and keeping the temperature at 70 DEGoDrying, calcining at 600 ℃ for 2h (the heating rate is 5 ℃ per min) in a muffle furnace, and naturally cooling to room temperature to obtain a white product, namely the rough-surface TiO2A nanoribbon.
Ammonium molybdate solution (250. mu.L) at a concentration of 27.22mg/mL was added to distilled water (60 mL), and after stirring for 30min, 0.1g of the TiO prepared above was added2The nanobelt is continuously stirred for 1 hour to ensure that ammonium molybdate is uniformly dispersed in TiO2Adding 250 μ L of the nano-belt surfaceAdjusting the pH value (pH = 6) of a mixed system by using a silver nitrate solution with the concentration of 26.19mg/mL, continuously stirring for 2h, transferring the liquid into a reaction kettle, keeping the temperature at 150 ℃ for 12h, cooling to room temperature, washing with deionized water, and drying to obtain Ag2Mo2O7/TiO2And (3) a bacteriostatic material. Pure Ag2Mo2O7Without adding TiO2Under the conditions of (1).
Ag2Mo2O7/TiO2Characterization of the bacteriostatic material:
FIG. 1 shows TiO prepared in this example2、Ag2Mo2O7And Ag2Mo2O7/TiO2FESEM image of (g). From the figure, it can be seen that TiO2The structure is in a band-shaped structure, the surface is rough, and more active sites can be provided for the reaction. Pure Ag2Mo2O7Is in a rod-shaped structure, and the width of the rod-shaped structure is 1-3 mu m. Ag2Mo2O7/TiO2No Ag was observed in the bacteriostatic material2Mo2O7Due to the rod-like structure of TiO2The particles on the surface of the nano belt provide more reaction sites for reaction, so that Ag+Is uniformly distributed in TiO2Surface of, lead to Ag2Mo2O7Uniformly and tightly growing on TiO in the form of nano particles2A nanoribbon surface.
FIG. 2 shows TiO prepared in this example2、Ag2Mo2O7And Ag2Mo2O7/TiO2XPS spectra of (a). As can be seen from FIG. 2a, Ag2Mo2O7/TiO2 Ti 2p in bacteriostatic material3/2And Ti 2p1/2The binding energy positions are 458.6eV and 464.3eV respectively, compared with pure TiO2Middle Ti4+ Ti 2p of3/2And Ti 2p1/2Low, indicating Ag2Mo2O7And TiO2A heterojunction is formed between them. Pure TiO2The bonding energy of the mesolattice oxygen and the surface adsorbed-OH is 530.0eV and 531.3eV respectively, and the Ag is2Mo2O7The binding energy of the medium O1 s is 530.3eV and 531.5eV respectively, while that of Ag2Mo2O7/TiO2The binding energy of O1 s in the antibacterial material is lower than that of pure TiO2And Ag2Mo2O7Further describe Ag2Mo2O7And TiO2Between which a heterojunction is formed (figure 2 b). As can be seen from FIGS. 2c-d, it is found that the Ag is pure Ag2Mo2O7In contrast, Ag2Mo2O7/TiO2The binding energy of Mo 3d in the antibacterial material is lower than that of pure Ag2Mo2O7And Ag is+Ag3d (g)5/2And Ag3d3/2The bonding energy of the Ag is higher than that of pure Ag2Mo2O7. The combination energy of the four elements of Ti, O, Ag and Mo is shifted simultaneously, which shows that TiO2And Ag2Mo2O7There is an interaction between them, forming a heterojunction.
FIG. 3 shows TiO prepared in this example2、Ag2Mo2O7And Ag2Mo2O7/TiO2XRD pattern of (a). Pure TiO in the figure2Has diffraction peak positions of 25.28 DEG, 37.80 DEG and 48.05 DEG, respectively, corresponding to the (101), (004) and (200) crystal planes, respectively, and anatase TiO2(JCPDS No. 78-2486) was completely anastomotic. Pure Ag2Mo2O7Diffraction peak positions were 14.00 °, 23.52 °, 28.31 °, 32.51 °, and 32.90 ° (JCPDS No. 75-1505), respectively. In Ag2Mo2O7/TiO2TiO is clearly observed in the sample2No diffraction peak of Ag was observed2Mo2O7May be due to Ag2Mo2O7Less content.
FIG. 4 shows TiO prepared in this example2、Ag2Mo2O7And Ag2Mo2O7/TiO2UV-vis spectrum of (1). As can be seen, pure TiO2The absorption band edge of (2) is about 400nm, and only ultraviolet light can be absorbed. Ag2Mo2O7Has an absorption band edge of about 490 nm. With pure TiO2In contrast, Ag2Mo2O7/TiO2Of bacteriostatic materialsThe absorption band edge is obviously red-shifted, which shows that the photoresponse range of the material is wider than that of TiO2And (4) wide.
FIG. 5 shows TiO prepared in this example2、Ag2Mo2O7And Ag2Mo2O7/TiO2Photocurrent response curve and alternating current impedance plot (EIS). As can be seen from FIG. 6a, Ag2Mo2O7/TiO2The photocurrent signal of the antibacterial material is obviously stronger than that of pure TiO2And Ag2Mo2O7The strongest photocurrent signal of AMT-10 indicates Ag2Mo2O7/TiO2The charge separation performance of the antibacterial material is the best. As shown in FIG. 6b, Ag2Mo2O7/TiO2The arc radius of the alternating current impedance curve of the antibacterial material is minimum, which shows that the impedance of charge transfer is minimum and the charge separation degree is highest.
And (3) bacteriostatic test:
the specific sterilization process is as follows: 50 mu L of Ag2Mo2O7/TiO2Adding bacteriostatic material dispersion (4 mg/mL) to 1.6X 106In cfu/mL of the bacterial suspension (10 mL), irradiation was performed using a 300W xenon lamp as a light source, and an AM1.5G filter was attached to the base of the light source. 500. mu.L of the sample was taken every 30min and diluted with 0.85wt% physiological saline. Then adding 1mL of diluted liquid into a culture plate, pouring 10-13mL of solid culture medium, transferring the culture medium into a constant temperature incubator, and culturing at 37 ℃ for 24 h. The number of colonies formed in each case was counted. The sterilization experiments are carried out in three parallel experiments, and the final experimental data is the average value of the three experimental data.
FIG. 6 is TiO2、Ag2Mo2O7And Ag2Mo2O7/TiO2The inactivation effect on Escherichia coli is shown. As can be seen from FIG. 6a, the prepared material has no obvious effect of inactivating bacteria under dark conditions, which indicates that Ag2Mo2O7/TiO2The bacteriostatic material has low toxicity to escherichia coli cells. TiO 60min in simulated sunlight (FIG. 6 b)2And Ag2Mo2O7Of living cells in the systemThe amounts were 6.5log and 6.7log, respectively, for Ag2Mo2O7/TiO2The antibacterial material can completely inactivate escherichia coli, which shows that Ag2Mo2O7/TiO2The antibacterial material has higher photocatalytic sterilization activity. This is probably due to Ag2Mo2O7And TiO2A heterojunction is formed between the two, and the effective separation of photo-generated charges is promoted.
FIG. 7 is a drawing through Ag2Mo2O7/TiO2FESEM image of treated E.coli. Coli, which had not been subjected to light treatment, had a smooth surface, a length of about 1-2 μm and a complete structure (FIG. 7 a). After 5 minutes of light, pits appeared on the surface of the bacteria (FIG. 7 a), indicating that the cell wall and cell membrane of E.coli began to be oxidized by the active species in the system. As the light exposure time was prolonged, the cells became severely deformed (FIGS. 7 c-e), and the E.coli cells became completely deformed when irradiated for 60 minutes (FIG. 7 f).
Various modifications may be made to the above without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is therefore intended to be limited not by the above description, but rather by the scope of the appended claims.
Claims (5)
1. Ag2Mo2O7/TiO2The preparation method of the antibacterial material is characterized by comprising the following specific steps:
step S1: dispersing P25 into a NaOH solution, carrying out hydrothermal reaction at 180 ℃ for 48h, cooling to room temperature, washing with deionized water to neutrality, dispersing in a hydrochloric acid solution, stirring for 24h, adding the material treated by the hydrochloric acid solution into a strong acid solution, stirring, and carrying out hydrothermal reaction at 100 DEG CoC, reacting for 12 hours, washing to be neutral by water, and reacting at 70 DEGoC, drying, heating to 500 ℃ at a heating rate of 5 ℃/min in a muffle furnace, calcining for 2h, and naturally cooling to room temperature to obtain a white product, namely the rough-surface TiO2A nanoribbon;
step S2: TiO obtained in step S12Dispersing the nanobelt into ammonium molybdate solution, stirring,adding a silver nitrate solution, adjusting the pH value of the mixed system to be 6, continuously stirring for 2h, transferring the obtained suspension into a reaction kettle, reacting at 150 ℃ for 12h, cooling to room temperature, centrifuging, washing and drying to obtain Ag2Mo2O7/TiO2And (3) a bacteriostatic material.
2. Ag according to claim 12Mo2O7/TiO2The preparation method of the antibacterial material is characterized by comprising the following steps: the concentration of the hydrochloric acid solution in step S1 was 0.1M.
3. Ag according to claim 12Mo2O7/TiO2The preparation method of the antibacterial material is characterized by comprising the following steps: the strong acid solution in step S1 is a 0.02M sulfuric acid solution.
4. Ag prepared by the method of any one of claims 1 to 32Mo2O7/TiO2Bacteriostatic material of Ag2Mo2O7/TiO2TiO in bacteriostatic material2And Ag2Mo2O7A heterojunction is formed between the two, the separation of the widely generated electron-hole pairs is promoted, and Ag is greatly inhibited2Mo2O7The stability of the heterojunction material is improved.
5. Ag according to claim 42Mo2O7/TiO2The antibacterial material is applied to photocatalytic inactivation of escherichia coli.
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