CN108772084A - TiO with photocatalysis antibacterial performance2/Cu2(OH)2CO3The preparation method and application of composite nano materials - Google Patents
TiO with photocatalysis antibacterial performance2/Cu2(OH)2CO3The preparation method and application of composite nano materials Download PDFInfo
- Publication number
- CN108772084A CN108772084A CN201810579036.8A CN201810579036A CN108772084A CN 108772084 A CN108772084 A CN 108772084A CN 201810579036 A CN201810579036 A CN 201810579036A CN 108772084 A CN108772084 A CN 108772084A
- Authority
- CN
- China
- Prior art keywords
- tio
- nano materials
- preparation
- photocatalysis antibacterial
- composite nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 38
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000011941 photocatalyst Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000002474 experimental method Methods 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 241000894006 Bacteria Species 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000012546 transfer Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000004599 antimicrobial Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 1
- 230000001954 sterilising effect Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 238000011109 contamination Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000011734 sodium Substances 0.000 description 9
- 239000003643 water by type Substances 0.000 description 9
- 241000588724 Escherichia coli Species 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000004083 survival effect Effects 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 230000002147 killing effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000588722 Escherichia Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229940041514 candida albicans extract Drugs 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910021649 silver-doped titanium dioxide Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012137 tryptone Substances 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
Classifications
-
- B01J35/39—
-
- 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
- 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
- A01N59/20—Copper
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
- B01J27/236—Hydroxy carbonates
Abstract
The invention discloses a kind of TiO with photocatalysis antibacterial performance2/Cu2(OH)2CO3The preparation method and application of composite nano materials belongs to photocatalysis antibacterial material synthesis technical field.With nano-TiO2With Cu (NO3)2For primary raw material, a certain proportion of Na is added2CO3Solution, the TiO for by the method for water-bath obtaining that there is high antibacterial activity2/Cu2(OH)2CO3Composite nano materials.The present invention is by the method for growth in situ, in TiO2Nano grain surface grows Cu2(OH)2CO3Nano-cluster, method is simple, raw material is cheap and easy to get, and equipment and technical process are simple to operation；This method has many advantages, such as that small reagent contamination, the reproducible of reaction, preparation condition are mild.The TiO of gained2/Cu2(OH)2CO3Composite nano materials show good antibacterial and sterilization ability in photocatalysis antibacterial process, and performance is stable, reproducible.
Description
Technical field
The invention belongs to solar energy, catalysis material and technical field of environment pollution control, specially a kind of to be urged with light
Change the TiO of anti-microbial property2/Cu2(OH)2CO3Composite nano materials and preparation method thereof.
Background technology
Since Japanese Scientists Matsunaga [FEMS Microbiology letters, 1985, 29(1-2):
211-214] etc. report TiO for the first time2Under ultraviolet lighting have good bactericidal property after, photocatalyst-type anti-biotic material by
Researcher's greatly pays close attention to and has carried out extensive research.Studies have shown that photocatalysis antibacterial material not only has broad spectrum antibacterial
Can, each quasi-microorganism can be killed, and the harmful substance gone out to Microbiological release can make its complete oxidation point without specificity
Solution, does not cause secondary pollution.Therefore, photocatalysis antibacterial material has anti-microbial property height, persistent, low drug resistance, without dirt
Dye, nontoxic and broad-spectrum antiseptic the advantages that, make its water body purification field have good application prospect [Applied microbiology and biotechnology, 2011, 90(6): 1847-1868].Currently, TiO2Because of its chemical property
The advantages that stable, nontoxic, inexpensive, becomes most popular photocatalysis antibacterial material.However, simple TiO2Material internal produces
Raw light induced electron and hole is easier to compound, causes quantum efficiency and catalytic activity to decline, restricts the reality of its photocatalysis antibacterial
It applies on border.
In order to reach higher photocatalysis efficiency, many researchers are devoted to TiO2The study on the modification side of photochemical catalyst
Face.The study found that in TiO2The a small amount of noble metal of area load can effectively inhibit light induced electron and hole as co-catalyst
It is compound, to improve its photocatalysis performance.Zhao[Biomaterials, 2011, 32(24):5706-5716] etc. use light
Reduction method has synthesized Ag/TiO2Nanometer tube composite materials, composite material prepared by the display of antibacterial experiment result have extremely excellent
Antibacterial characteristics.But the price is very expensive for noble metal, and the cost for making co-catalyst using noble metal is higher, therefore is improving light
Cost is reduced while catalytic performance becomes a critically important research direction.Recently, Cu compound cocatalysts are due to honest and clean
Valence, efficiently, reported by many relevant reports.Xu[International Journal of Hydrogen Energy, 2010, 35(11):5254-5261] etc. report the TiO of composite Cu system co-catalyst2Catalysis material is even
Than the TiO of some noble-metal-supporteds2The photocatalysis efficiency higher of catalysis material.But up to the present, by TiO2/ Cu systems help
Research of the catalyst for photocatalysis antibacterial is not reported also.
Invention content
For existing TiO2That there are preparation processes is complicated for catalysis material, cost is higher and photo-generate electron-hole is to easily multiple
The shortcomings that conjunction, the technical problem to be solved by the present invention is to using easy lower one kind of method synthesis cost there is excellent light to urge
Change the TiO of anti-microbial property2/Cu2(OH)2CO3Composite nano materials and preparation method thereof.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of TiO with photocatalysis antibacterial performance2/Cu2(OH)2CO3The preparation method of composite nano materials, steps are as follows：
（1）By TiO2Nano particle is add to deionized water；Then Cu (NO are added3)2٠3H2O solids, after ultrasonic agitation is uniform
It transfers them to 10 min of constant temperature in 60 DEG C of water-baths and obtains mixed solution；
（2）By Na2CO3It is dissolved in deionized water, beaker, which is put into 10 min of constant temperature in 60 DEG C of water-baths, obtains Na2CO3It is molten
Liquid；
（3）By step（1）In mixed solution pour into step rapidly（2）In Na2CO3In solution, then in 60 DEG C of water-baths
Constant temperature stirs 30min in pot；After its reaction, product is centrifuged, is washed twice respectively with deionized water and absolute ethyl alcohol,
TiO is made in 60 DEG C of 12 h of drying in vacuum drying chamber2/Cu2(OH)2CO3Composite photocatalyst material.
The step（1）Middle Cu (NO3)2٠3H2O and TiO2The ratio between the amount of substance be 1:13.3~53.8.
Cu(NO3)2٠3H2O and Na2CO3The ratio between the amount of substance be 1: 1.2.
The TiO2/Cu2(OH)2CO3Cu in composite photocatalyst material2(OH)2CO3Molar content be 0.9% ~
3.6%。
The TiO with photocatalysis antibacterial performance2/Cu2(OH)2CO3Composite nano materials are as photocatalysis antibacterial agent
Application：By 10 mg TiO2/Cu2(OH)2CO3Composite photocatalyst material and 9.9 mL PBS are placed in the mm of 60 mm × 15
In plate, 10 min of Ultrasound Instrument ultrasound disperse mixing, and 0.1 mL a concentration of 10 is added later7The bacteria suspension of CFU/mL
It mixes well, is subsequently placed in progress photocatalysis antibacterial experiment under light source.
Beneficial effects of the present invention：1. the present invention utilizes TiO2、Cu(NO3)2٠3H2O and Na2CO3For presoma, by low
Tepidarium method has obtained TiO2/Cu2(OH)2CO3Composite photocatalyst material.
2. the method provided through the invention, the TiO of preparation2/Cu2(OH)2CO3Composite photocatalyst material is in simulated solar
There is good inhibition or killing performance to Escherichia coli under light.
3. raw material of the present invention is cheap, cost is relatively low, easy to operate, easily controllable.
Description of the drawings
Fig. 1 is the X-ray powder diffraction of different samples prepared by 1-5 of the embodiment of the present invention（XRD）Figure；
Fig. 2 is the TEM photos of composite material prepared by the embodiment of the present invention 3；
Fig. 3 is the EDX collection of illustrative plates of composite material prepared by the embodiment of the present invention 3；
Fig. 4 is the XPS collection of illustrative plates of composite material prepared by the embodiment of the present invention 3；
Fig. 5 is the antibacterial experiment result picture of composite material prepared by the embodiment of the present invention 3；
Fig. 6 is different samples prepared by 1-5 of the embodiment of the present invention and the photocatalysis antibacterial curve of check experiment.
Specific implementation mode
With reference to specific embodiment, the present invention will be further described.It should be understood that following embodiment is merely to illustrate this
The person skilled in the art of the range of invention and is not intended to limit the present invention, the field can make one according to the content of foregoing invention
A little nonessential modifications and adaptations.
Embodiment 1
Weigh the Cu (NO of 0.24 g (1 mmol)3)2٠3H2O solids are added in 20 mL deionized waters, and ultrasonic agitation is uniform
After transfer them to 10 min of constant temperature in 60 DEG C of water-baths；Weigh the Na of 0.13 g (1.2 mmol)2CO3It is dissolved in 24 ml
In deionized water, 10 min of constant temperature in 60 DEG C of water-baths is placed on after ultrasonic agitation is uniform.Then by Cu (NO3)2Aqueous solution is rapid
Pour into Na2CO3In aqueous solution, then constant temperature stirs 30 min in 60 DEG C of water-baths.After the completion of reaction, wait for that it is cooled to room
Temperature is washed twice respectively with deionized water and absolute ethyl alcohol, 60 DEG C of 12 h of drying in vacuum drying chamber, and Cu is made2(OH)2CO3
Material.
Embodiment 2
The TiO with photocatalysis antibacterial performance of the present embodiment2/Cu2(OH)2CO3The preparation method of composite nano materials, step
It is as follows：
（1）Weigh 4.30 g (53.8 mmol) TiO2Nano particle is added in 20 mL deionized waters；Then it is added 0.24
Cu (the NO of g (1 mmol)3)2٠3H2O solids transfer them to constant temperature 10 in 60 DEG C of water-baths after ultrasonic agitation is uniform
min；
（2）Weigh the Na of 0.13 g (1.2 mmol)2CO3It is dissolved in 24 ml deionized waters, beaker is put into 60 DEG C
10 min of constant temperature in water-bath；
（3）Then TiO will be filled2With Cu (NO3)2Mixed aqueous solution pour into Na rapidly2CO3In aqueous solution, in 60 DEG C of water
Constant temperature stirs 30 min in bath；Product is centrifuged after its reaction, two are washed respectively with deionized water and absolute ethyl alcohol
Secondary, TiO is made in 60 DEG C of 12 h of drying in vacuum drying chamber2/Cu2(OH)2CO3- 0.9% composite photocatalyst material.
The preparation of LB culture mediums：10 g of sodium chloride, 10 g of tryptone are weighed, 5 g of yeast extract adds water to 1000
ML adjusts its pH=7.0 with NaOH solution, obtains LB liquid medium；15 g agar are added into fluid nutrient medium, you can
To solid medium, culture medium is placed in 121 DEG C of high-pressure steam sterilizing pans 25 min that sterilize, refrigeration is spare.
Antibacterial experiment：1）The e. coli k12 bacterial strain of Storage in refrigerator is taken to cross 37 DEG C in solid LB culture medium flat plates
Overnight incubation, activation twice, take the single bacterium after activation to fall in liquid LB culture mediums 37 DEG C, 15 0 rpm shaking table cultures
12 h, twice, taking 6000 rpm of bacterium solution, 5 min of last time shaking table culture, thalline were collected by centrifugation is used in combination for shaking table culture
PBS buffer solution for cleaning three times, is finally suspended in PBS, and adjustment bacteria concentration is about 107CFU/mL is for photocatalysis
Experiment.Required consumptive material is placed in 121 DEG C of 30 min of sterilizing in autoclave in experiment.
2）The concentration of material therefor is 1 mg/mL in experiment.First, by 10 mg material powders and 9.9 mL PBS
It is placed in the mm plates of 60 mm × 15,10 min of Ultrasound Instrument ultrasound disperse mixing, and 0.1 mL a concentration of 10 is added later7
The bacteria suspension of CFU/mL mixes well, and is subsequently placed in progress photo-catalyst experiment under light source.Secondly, it is taken in different moments point
Go out 0.1 ml mixed liquors, be coated with uniformly on LB tablets after being diluted with PBS buffer gradients, after 37 DEG C of 24 h of culture
Calculate different moments point Escherichia coli single bacterium colony number and sterilizing rate.Check experiment includes pure TiO2And Cu2(OH)2CO3Under illumination
To the killing effect and TiO of Escherichia coli2/Cu2(OH)2CO3Escherichia coli deposits when unglazed irradiation is irradiated with only light without material
Situation living.In triplicate, entire experimental situation carries out at room temperature, and temperature is room temperature for all photocatalysis experiments.
XRD analysis is carried out to obtained sample using German Bruker companies D8 Advance types X-ray diffractometers.Fig. 1
For the XRD spectra of sample, show that the sample of preparation is pure phase Cu2(OH)2CO3.The antibacterial curve of Fig. 6 shows Cu2(OH)2CO3Material
Material is after 80 min of illumination, and there are about the survivals of 44.9% Escherichia coli, and photocatalysis antibacterial rate is only 55.1%.
Antibacterial curve shows（Fig. 6）, the present embodiment composite material shows good photocatalysis antibacterial under simulated solar irradiation
Performance, after reaction carries out 80 min, there are about the survival of the Escherichia coli of 1.2 log, photocatalysis antibacterial rate can reach 99.99%.
Embodiment 3
The TiO with photocatalysis antibacterial performance of the present embodiment2/Cu2(OH)2CO3The preparation method of composite nano materials, step
It is as follows：
（1）Weigh 2.15 g (26.9 mmol) TiO2Nano particle is added in 20 mL deionized waters；Then it is added 0.24
Cu (the NO of g (1 mmol)3)2٠3H2O solids transfer them to constant temperature 10 in 60 DEG C of water-baths after ultrasonic agitation is uniform
min；
（2）Weigh the Na of 0.13 g (1.2 mmol)2CO3It is dissolved in 24 ml deionized waters, beaker is put into 60 DEG C
10 min of constant temperature in water-bath；
（3）Then TiO will be filled2With Cu (NO3)2Mixed aqueous solution pour into Na rapidly2CO3In aqueous solution, in 60 DEG C of water
Constant temperature stirs 30 min in bath；Product is centrifuged after its reaction, two are washed respectively with deionized water and absolute ethyl alcohol
Secondary, TiO is made in 60 DEG C of 12 h of drying in vacuum drying chamber2/Cu2(OH)2CO3- 1.8% composite photocatalyst material.
Schemed by TEM（Fig. 2）, it can be found that in TiO2Nano grain surface loads the nano-cluster for having 1-2 nm, by EDX
Prove that it is Cu with XPS tests2(OH)2CO3Nano-cluster（Fig. 3 and Fig. 4）.
Photocatalysis antibacterial the experimental results showed that, Cu2(OH)2CO3Nano-cluster loads TiO2Photocatalysis antibacterial performance carry significantly
It is high.As shown in figure 5, original content is 107 cfu mL-1Escherichia coli after 80 min of illumination, be almost killed.It compares
In simple TiO2And Cu2(OH)2CO3, photocatalysis sterilization effect improves 6 log units.This kind of composite material photocatalysis is killed
Active significantly improve of bacterium is mainly due to Cu2(OH)2CO3TiO can be captured as co-catalyst2Electronics on conduction band, from
And effectively inhibit TiO2Electrons and holes it is compound, be conducive to the separation of photo-generate electron-hole pair.
Embodiment 4
The TiO with photocatalysis antibacterial performance of the present embodiment2/Cu2(OH)2CO3The preparation method of composite nano materials, step
It is as follows：
（1）Weigh 1.45 g (18.2 mmol) TiO2Nano particle is added in 20 mL deionized waters；Then it is added 0.24
Cu (the NO of g (1 mmol)3)2٠3H2O solids transfer them to constant temperature 10 in 60 DEG C of water-baths after ultrasonic agitation is uniform
min；
（2）Weigh the Na of 0.13 g (1.2 mmol)2CO3It is dissolved in 24 ml deionized waters, beaker is put into 60 DEG C
10 min of constant temperature in water-bath；
（3）Then TiO will be filled2With Cu (NO3)2Mixed aqueous solution pour into Na rapidly2CO3In aqueous solution, in 60 DEG C of water-baths
Constant temperature stirs 30 min in pot；Product is centrifuged after its reaction, is washed twice respectively with deionized water and absolute ethyl alcohol,
TiO is made in 60 DEG C of 12 h of drying in vacuum drying chamber2/Cu2(OH)2CO3- 2.7% composite photocatalyst material.
Embodiment 5
The TiO with photocatalysis antibacterial performance of the present embodiment2/Cu2(OH)2CO3The preparation method of composite nano materials, step
It is as follows：
（1）Weigh 1.06 g (13.3 mmol) TiO2Nano particle is added in 20 mL deionized waters；Then it is added 0.24
Cu (the NO of g (1 mmol)3)2٠3H2O solids transfer them to constant temperature 10 in 60 DEG C of water-baths after ultrasonic agitation is uniform
min；
（2）Weigh the Na of 0.13 g (1.2 mmol)2CO3It is dissolved in 24 ml deionized waters, beaker is put into 60 DEG C
10 min of constant temperature in water-bath；
（3）Then TiO will be filled2With Cu (NO3)2Mixed aqueous solution pour into Na rapidly2CO3In aqueous solution, in 60 DEG C of water-baths
Constant temperature stirs 30 min in pot；Product is centrifuged after its reaction, is washed twice respectively with deionized water and absolute ethyl alcohol,
TiO is made in 60 DEG C of 12 h of drying in vacuum drying chamber2/Cu2(OH)2CO3- 3.6% composite photocatalyst material.Antibacterial curve table
It is bright（Fig. 6）, this kind of composites show preferable photocatalysis antibacterial performance under simulated solar irradiation.After 80 min of illumination,
The only about Escherichia coli survival of 3.48 log.
The basic principles and main features and advantages of the present invention of the present invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (5)
1. a kind of TiO with photocatalysis antibacterial performance2/Cu2(OH)2CO3The preparation method of composite nano materials, it is characterised in that
Steps are as follows：
（1）By TiO2Nano particle is add to deionized water；Then Cu (NO are added3)2٠3H2O solids, after ultrasonic agitation is uniform
It transfers them to 10 min of constant temperature in 60 DEG C of water-baths and obtains mixed solution；
（2）By Na2CO3It is dissolved in deionized water, beaker, which is put into 10 min of constant temperature in 60 DEG C of water-baths, obtains Na2CO3It is molten
Liquid；
（3）By step（1）In mixed solution pour into step rapidly（2）In Na2CO3In solution, then in 60 DEG C of water-baths
Middle constant temperature stirs 30min；After its reaction, product is centrifuged, is washed twice respectively with deionized water and absolute ethyl alcohol,
TiO is made in 60 DEG C of 12 h of drying in vacuum drying chamber2/Cu2(OH)2CO3Composite photocatalyst material.
2. the TiO described in accordance with the claim 1 with photocatalysis antibacterial performance2/Cu2(OH)2CO3The preparation of composite nano materials
Method, it is characterised in that：The step（1）Middle Cu (NO3)2٠3H2O and TiO2The ratio between the amount of substance be 1:13.3~53.8.
3. the TiO described in accordance with the claim 1 with photocatalysis antibacterial performance2/Cu2(OH)2CO3The preparation of composite nano materials
Method, it is characterised in that：Cu(NO3)2٠3H2O and Na2CO3The ratio between the amount of substance be 1: 1.2.
4. the TiO described in accordance with the claim 1 with photocatalysis antibacterial performance2/Cu2(OH)2CO3The preparation of composite nano materials
Method, it is characterised in that：The TiO2/Cu2(OH)2CO3Cu in composite photocatalyst material2(OH)2CO3Molar content be
0.9%~3.6%。
5. the TiO described in accordance with the claim 1 with photocatalysis antibacterial performance2/Cu2(OH)2CO3Composite nano materials are as light
The application of catalytic antimicrobial agent：By 10 mg TiO2/Cu2(OH)2CO3Composite photocatalyst material and 9.9 mL PBS are placed in 60
In the mm plates of mm × 15,10 min of Ultrasound Instrument ultrasound disperse mixing, and 0.1 mL a concentration of 10 is added later7 CFU/mL
Bacteria suspension mix well, be subsequently placed under light source progress photocatalysis antibacterial experiment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810579036.8A CN108772084B (en) | 2018-06-07 | 2018-06-07 | TiO with photocatalytic antibacterial property2/Cu2(OH)2CO3Preparation method and application of composite nano material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810579036.8A CN108772084B (en) | 2018-06-07 | 2018-06-07 | TiO with photocatalytic antibacterial property2/Cu2(OH)2CO3Preparation method and application of composite nano material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108772084A true CN108772084A (en) | 2018-11-09 |
| CN108772084B CN108772084B (en) | 2021-06-18 |
Family
ID=64024759
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810579036.8A Active CN108772084B (en) | 2018-06-07 | 2018-06-07 | TiO with photocatalytic antibacterial property2/Cu2(OH)2CO3Preparation method and application of composite nano material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108772084B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110252310A (en) * | 2019-06-26 | 2019-09-20 | 郑州轻工业学院 | A kind of auto-dope TiO with anti-microbial property2The preparation method of/Ni nanocomposite |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1692735A (en) * | 2005-05-20 | 2005-11-09 | 东北大学 | Antibiosis material of low cost, and its prepn. method |
| CN102076610A (en) * | 2008-07-08 | 2011-05-25 | 巴斯夫欧洲公司 | Nanoparticulate surface-modified copper compounds |
| CN102275973A (en) * | 2011-06-01 | 2011-12-14 | 华南师范大学 | Preparation method of basic copper carbonate microspheres |
| CN105047421A (en) * | 2015-06-15 | 2015-11-11 | 昆明理工大学 | Method for preparing graphene/basic carbonate nanocomposite material |
| CN105107504A (en) * | 2015-09-11 | 2015-12-02 | 江苏锦宇环境工程有限公司 | Preparing method for photocatalyst/copper oxide compound light photocatalytic material |
| CN106687459A (en) * | 2014-08-13 | 2017-05-17 | Sds生物技术株式会社 | Fused 11-membered compounds and agricultural/horticultural fungicides containing them |
| CN106732590A (en) * | 2016-11-24 | 2017-05-31 | 郑州轻工业学院 | A kind of preparation method of copper/titanium oxide photochemical catalyst nano material |
| CN106824233A (en) * | 2017-03-27 | 2017-06-13 | 曲靖师范学院 | The method of photocatalysis antibacterial or degradation of organic substances |
| CN106944150A (en) * | 2017-04-26 | 2017-07-14 | 沈阳工业大学 | The compound of copper bismuth bimetallic coordination polymer and graphene and its preparation method |
-
2018
- 2018-06-07 CN CN201810579036.8A patent/CN108772084B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1692735A (en) * | 2005-05-20 | 2005-11-09 | 东北大学 | Antibiosis material of low cost, and its prepn. method |
| CN102076610A (en) * | 2008-07-08 | 2011-05-25 | 巴斯夫欧洲公司 | Nanoparticulate surface-modified copper compounds |
| CN102275973A (en) * | 2011-06-01 | 2011-12-14 | 华南师范大学 | Preparation method of basic copper carbonate microspheres |
| CN106687459A (en) * | 2014-08-13 | 2017-05-17 | Sds生物技术株式会社 | Fused 11-membered compounds and agricultural/horticultural fungicides containing them |
| CN105047421A (en) * | 2015-06-15 | 2015-11-11 | 昆明理工大学 | Method for preparing graphene/basic carbonate nanocomposite material |
| CN105107504A (en) * | 2015-09-11 | 2015-12-02 | 江苏锦宇环境工程有限公司 | Preparing method for photocatalyst/copper oxide compound light photocatalytic material |
| CN106732590A (en) * | 2016-11-24 | 2017-05-31 | 郑州轻工业学院 | A kind of preparation method of copper/titanium oxide photochemical catalyst nano material |
| CN106824233A (en) * | 2017-03-27 | 2017-06-13 | 曲靖师范学院 | The method of photocatalysis antibacterial or degradation of organic substances |
| CN106944150A (en) * | 2017-04-26 | 2017-07-14 | 沈阳工业大学 | The compound of copper bismuth bimetallic coordination polymer and graphene and its preparation method |
Non-Patent Citations (2)
| Title |
|---|
| ZHIKANG HE ET AL.: "Cu2(OH)2CO3 clusters: Novel noble-metal-free cocatalysts for efficient photocatalytic hydrogen production from water splitting", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| 薛永飞: "可见光响应TiO2光催化材料的制备及其应用研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110252310A (en) * | 2019-06-26 | 2019-09-20 | 郑州轻工业学院 | A kind of auto-dope TiO with anti-microbial property2The preparation method of/Ni nanocomposite |
| CN110252310B (en) * | 2019-06-26 | 2022-04-15 | 郑州轻工业学院 | Self-doped TiO with antibacterial property2Preparation method of/Ni nano composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108772084B (en) | 2021-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ding et al. | Visible light responsive CuS/protonated g-C3N4 heterostructure for rapid sterilization | |
| Rahmati et al. | Ag-doped magnetic metal organic framework as a novel nanostructured material for highly efficient antibacterial activity | |
| CN111248224B (en) | Preparation method and antibacterial activity test method of antibacterial agent based on MXene quantum dots | |
| CN110449169B (en) | Semi-metal material Te nanowire/graphene hydrogel composite material and preparation method and application thereof | |
| Wang et al. | Unveiling the visible–light–driven photodegradation pathway and products toxicity of tetracycline in the system of Pt/BiVO4 nanosheets | |
| Li et al. | Enhanced simultaneous PEC eradication of bacteria and antibiotics by facilely fabricated high-activity {001} facets TiO2 mounted onto TiO2 nanotubular photoanode | |
| CN102974375B (en) | Multifunctional composite material with heterostructure and preparation method thereof | |
| CN101171929A (en) | Method for preparing nano silver antimicrobials | |
| CN108822838B (en) | Preparation method and application of copper-doped carbon quantum dots | |
| Li et al. | Fabrication of carbon quantum dots/1D MoO3-x hybrid junction with enhanced LED light efficiency in photocatalytic inactivation of E. ácoli and S. áaureus | |
| CN107243348A (en) | A kind of biological assisted synthesizing method of biocidal property photochemical catalyst | |
| CN105724372B (en) | A kind of support type ZnO antimicrobial composite materials and preparation method thereof | |
| CN110115272A (en) | A kind of Cu nanoparticle coupling graphene hydrogel composite material and its preparation method and application | |
| Zhang et al. | Extensive solar light utilizing by ternary C-dots/Cu2O/SrTiO3: Highly enhanced photocatalytic degradation of antibiotics and inactivation of E. coli | |
| CN109603906B (en) | Anthraquinone-2-sodium sulfonate/graphene oxide composite photocatalytic bactericide and preparation method and application thereof | |
| Kumar et al. | Photocatalytic disinfection of water with Ag–TiO 2 nanocrystalline composite | |
| CN111528223A (en) | Composite antibacterial material with slow-release chlorine dioxide and preparation method thereof | |
| CN101532176B (en) | Preparation method of polycrystal nano calcium aluminum oxide | |
| CN108772084A (en) | TiO with photocatalysis antibacterial performance2/Cu2(OH)2CO3The preparation method and application of composite nano materials | |
| CN112375804B (en) | Au/g-C 3 N 4 All-weather photocatalytic antibacterial material and light-dark dual-mode antibacterial mechanism thereof | |
| CN109621932A (en) | White carbon black-titanic oxide composite photochemical catalyst antibacterial agent preparation method | |
| CN101518259B (en) | Antibacterial application of polycrystalline nanometer calcium-aluminum oxide | |
| CN102085481A (en) | Preparation and application of composite photo-catalysis bactericide for visible light response | |
| CN109964957A (en) | A kind of Cu2The environment-friendly preparation method thereof of O/Ag nano anti-biotic material | |
| Huang et al. | Visible-light photocatalytic properties and biological effects of BiOI modified using a bismuth metal-organic framework |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |