CN104923205B - Titanium dioxide antibiotic removes formaldehyde composite material and preparation method and purposes - Google Patents
Titanium dioxide antibiotic removes formaldehyde composite material and preparation method and purposes Download PDFInfo
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 126
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 27
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 21
- 238000002525 ultrasonication Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 9
- 239000003973 paint Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 26
- 229910052980 cadmium sulfide Inorganic materials 0.000 abstract description 25
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 5
- 239000007790 solid phase Substances 0.000 abstract description 4
- 239000003242 anti bacterial agent Substances 0.000 abstract description 2
- 229940088710 antibiotic agent Drugs 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract 1
- 230000000844 anti-bacterial effect Effects 0.000 description 23
- 239000000463 material Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 11
- 241000894006 Bacteria Species 0.000 description 10
- 239000010410 layer Substances 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 230000003385 bacteriostatic effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000005215 recombination Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 241000588724 Escherichia coli Species 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000006798 recombination Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 241000191967 Staphylococcus aureus Species 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 241000235527 Rhizopus Species 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000228245 Aspergillus niger Species 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 206010003694 Atrophy Diseases 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000037444 atrophy Effects 0.000 description 2
- 235000008429 bread Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
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- 235000015097 nutrients Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
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- 239000011941 photocatalyst Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000228212 Aspergillus Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- -1 Graphite alkene Chemical class 0.000 description 1
- 241000896292 Odontothrips loti Species 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical class O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
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- 230000002779 inactivation Effects 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
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Abstract
The invention discloses a kind of titanium dioxide antibiotics to remove formaldehyde composite material and preparation method and purposes, and by weight percentage, the titanium dioxide antibiotic becomes except the group of formaldehyde composite material：Titanium dioxide 10% 20%；Redox graphene (RGO) 1% 10%；Cadmium sulfide 70% 89%.The preparation method includes：(1) aqueous solution containing titanium dioxide, redox graphene, cadmium sulfide respectively is provided；(2) three kinds of aqueous solutions are mixed, is centrifugally separating to obtain solid phase, solid phase is washed, dry, roasting, and the titanium dioxide antibiotic is made except formaldehyde composite material.The invention also discloses the coating that formaldehyde composite material is removed comprising a kind of titanium dioxide antibiotic.The present invention is compound by redox graphene, cadmium sulfide and titanium dioxide, utilize the good electric conductivity of redox graphene, the transmission for promoting light induced electron, reduces the compound probability in light induced electron and hole, and then improves bacteriostasis rate and formaldehyde removal rate.
Description
Technical field
The present invention relates to a kind of antibacterial except formaldehyde materials more particularly to a kind of titanium dioxide antibiotic except formaldehyde composite material and
Preparation method and use.
Background technology
1972, Japanese Fujishima etc. existed《Nature》" TiO has been delivered on magazine2Photocatalytic water on an electrode " text,
The prelude of photocatalysis oxidation technique is opened.In numerous photochemical catalysts, TiO2With its, chemical stabilization higher with catalytic capability
Property it is good, resistance to acid and alkali is good, nontoxic, cheap the advantages that and become most common photochemical catalyst.
Due to TiO2Photochemical catalyst greater band gap (3.2eV) can only excite (λ by the shorter ultraviolet light of wavelength<
387nm), and in visible light ultraviolet light (400nm or less) only accounts for 5%, and wavelength is that the visible light of 400-750nm then accounts for
45%, therefore visible light utilization efficiency is very low, simultaneously as the electronics (e that light excitation generates-) hole (h+) it is compound, lead to light quantity
Sub- efficiency is very low.In recent years, various countries researcher is dedicated to TiO2The metal of photochemical catalyst or it is nonmetallic ion-doped, semiconductor is multiple
It closes and promotes TiO with means such as surface modifications2Photochemical catalyst it is visible light-responded, and reduce the compound of electron hole pair and improve
The activity of catalyst material and avoid TiO2The inactivation of photochemical catalyst.
(1) nonmetal doping is modified.The visible light for realizing semiconductor light-catalyst is adulterated by nonmetallic (N, S, C, F etc.)
Change is a current research hotspot both domestic and external.Wherein, good modified effect is shown with N element doping.Asahi in 2001
It is a kind of in visible light (λ etc. reporting<There is the TiO of very highlight catalytic active and Superhydrophilic under 500nm)2-xNx(x=
0.75%) powder and film photocatalyst, nitrogen replace a small amount of Lattice Oxygen that can make TiO2Band gap narrow, and do not reducing purple
It is outer photoactive while realizing that visible light photocatalysis responds, pull open the prelude of N doping or even nonmetal doping photochemical catalyst
(Science,2001,293(5528):269-271.).Currently, being mainly according to different nitrogen sources to the research of N doping method
Design differential responses with titanium source (or other transition metal), mainly have Gas-solid phase reaction, solid phase reaction, liquid phase reactor,
High-temperature spray decomposition reaction etc..
(2) transient metal doped or composite modified.Since there are more chemical valences for transition metal element, in TiO2It is mixed in lattice
Miscellaneous a small amount of transition metal ions, you can generate defect on its surface or change its crystallinity, become the shallow of photo-generate electron-hole pair
Gesture captures trap, extends the recombination time of electronics and hole, makes TiO2It shows p-n junction photoresponse and phenomenon coexists, reduce photoproduction electricity
The recombination probability in son-hole, to improve TiO2Photocatalytic activity.Choil etc. systematically has studied 21 metal ion species and mixes
Miscellaneous TiO2, find to adulterate the Fe that mass fraction is 0.1%-0.5% in lattice3+、Mo5+、Ru2+、Os2+、V5+And Rh2+Enhancing
TiO2Photocatalytic activity, and think the concentration of dopant, the distribution of Doped ions, doped energy-band and TiO2Energy band matching degree,
The configuration of Doped ions d electronics, the transfer of charge and the factors such as compound have a direct impact the photocatalytic activity of catalyst
(Journal of Physical Chemistry,1994,98(5):13669-13679.).Wu Shu is newly equal using dipping legal system
For transient metal doped photochemical catalyst MOx/TiO2(M=Cr, Mn, Fe, Co, Ni, Cu), result of study show through transition gold
Belong to the TiO of doping vario-property2, photocatalysis performance all increases, and obtains doping there are an optimum value (physical chemistry
Report, 2004,20 (20):138-143.).
However, the light induced electron efficiency of transmission of the above modified titanium dioxide photocatalyst is relatively low, and easily and hole-recombination, after
And its antibacterial and except effect of formaldehyde it is unsatisfactory.
Invention content
The present invention provides a kind of titanium dioxide antibiotics to remove formaldehyde composite material, is urged with solving existing modifying titanium dioxide light
Agent antibacterial and except the not good enough problem of effect of formaldehyde.
A kind of titanium dioxide antibiotic removes formaldehyde composite material, and by weight percentage, group becomes：Titanium dioxide 10%-
20%；Redox graphene (RGO) 1%-10%；Cadmium sulfide 70%-89%.
Further preferably, titanium dioxide 12%-20%；Redox graphene 3%-8%；Cadmium sulfide 75%-85%.
Most preferably, titanium dioxide 15%；Redox graphene 5%；Cadmium sulfide 80%.
The present invention also provides the preparation methods that the titanium dioxide antibiotic removes formaldehyde composite material, including：
(1) aqueous solution containing titanium dioxide, redox graphene, cadmium sulfide respectively is provided；
(2) three kinds of aqueous solutions are mixed, is centrifugally separating to obtain solid phase, solid phase is washed, dry, roasting, the obtained oxygen
Change titanium antibacterial and removes formaldehyde composite material.
To further increase dispersion effect ultrasonication 10-60min is utilized after aqueous solution mixing.
Preferably, the temperature of the roasting is 300-500 DEG C.
Invention further provides a kind of coating, it includes that the titanium dioxide antibiotic removes formaldehyde composite material.
Preferably, the weight percent that the titanium dioxide antibiotic removes formaldehyde composite material is 1%-5%.
The present invention is compound by redox graphene, cadmium sulfide and titanium dioxide, good using redox graphene
Electric conductivity, promote the transmission of light induced electron, reduce light induced electron and the recombination probability in hole, and then improve antibacterial
Rate.
Antibacterial of the present invention inhibits the effect of rhizopus growth except formaldehyde composite material is not only demonstrated by well, but also it is not
It can be interfered by coating mixing, being coated on aluminium sheet has apparent antibacterial action, and in addition composite material of the present invention has good
Degradation of formaldehyde performance, be applied to household material potential quality it is big.
Description of the drawings
Fig. 1 is bacteriostatic experiment result of 8 kinds of materials to Escherichia coli.
Fig. 2 is bacteriostatic experiment result of 8 kinds of materials to staphylococcus aureus.
Fig. 3 is bacteriostatic experiment result of 8 kinds of materials to aspergillus niger.
Fig. 4 is bacteriostatic experiment result of 8 kinds of materials to bread mold.
Fig. 5 is the SEM figures before and after composite material of the present invention effect Escherichia coli, before (a)；(b) after.
Fig. 6 is the SEM figures before and after composite material of the present invention effect staphylococcus aureus, before (a)；(b) after.
Fig. 7 is the bacteriostatic experiment result for being coated with composite material and uncoated composite material aluminium sheet to aspergillus niger.
Fig. 8 is composite material, composite material and paints the bacteriostatic experiment result for mixing ovendry power foot couple bread mold.
Fig. 9 is that the antibacterial of different redox graphene contents removes the change of the Degradation Formaldehyde rate of formaldehyde composite material at any time
Change curve.
Figure 10 is antibacterial made of different calcination atmospheres except the Degradation Formaldehyde rate of formaldehyde composite material changes with time song
Line.
Figure 11 is the Degradation Formaldehyde rate versus time curve that bacterium removes formaldehyde composite material made of different calcination temperatures.
Specific implementation mode
Embodiment 1
(1)0.2g TiO2(being purchased from Sinopharm Chemical Reagent Co., Ltd.) and 10mL water mix, ultrasonication 30min；
(2) 0.064g redox graphenes (RGO) and the mixing of 15mL water, ultrasonication 30min；
(3) above two solution is mixed, ultrasonication 30min；
(4) 1.6g CdCl are weighed2·2.5H2O (0.007mol) is added in the mixed solution of step (3), stirring
30min；
(5) 1.7g Na are weighed2S·9H2O (0.007mol) is dissolved in 25mL water, then is added dropwise to the solution of step (4)
In, generate CdS.
(6) continue stirring 2 days.
(7) it centrifuges, extraction lower layer solid is washed 3-5 times, dry, N2Under atmosphere (flow 0.5mL/min), 400 DEG C of roastings
It burns 4 hours, obtains TiO2-RGO-CdS。
Embodiment 2
(1)0.2g TiO2(being purchased from Sinopharm Chemical Reagent Co., Ltd.) and 10mL water mix, ultrasonication 30min；
(2) 0.09g redox graphenes and the mixing of 15mL water, ultrasonication 30min；
(3) above two solution is mixed, ultrasonication 30min；
(4) 1.6g CdCl are weighed2·2.5H2O (0.007mol) is added in the mixed solution of step (3), stirring
30min；
(5) 1.7g Na are weighed2S·9H2O (0.007mol) is dissolved in 25mL water, then is added dropwise to the solution of step (4)
In, generate CdS；
(6) continue stirring 2 days；
(7) it centrifuges, extraction lower layer solid is washed 3-5 times, dry, N2Under atmosphere (flow 0.5mL/min), 400 DEG C of roastings
It burns 4 hours, obtains TiO2-RGO-CdS。
Embodiment 3
(1)0.2g TiO2(being purchased from Sinopharm Chemical Reagent Co., Ltd.) and 10mL water mix, ultrasonication 30min；
(2) 0.037g redox graphenes and the mixing of 15mL water, ultrasonication 30min；
(3) above two solution is mixed, ultrasonication 30min；
(4) 1.6g CdCl are weighed2·2.5H2O (0.007mol) is added in the mixed solution of step (3), stirring
30min；
(5) 1.7g Na are weighed2S·9H2O (0.007mol) is dissolved in 25mL water, then is added dropwise to the solution of step (4)
In, generate CdS.
(6) continue stirring 2 days.
(7) it centrifuges, extraction lower layer solid is washed 3-5 times, dry, N2Under atmosphere (flow 0.5mL/min), 400 DEG C of roastings
It burns 4 hours, obtains TiO2-RGO-CdS。
Embodiment 4
(1) 1.6g CdCl are weighed2·2.5H2O (0.007mol) is dissolved in water, stirs 30min；
(2) 1.7g Na are weighed2S·9H2O (0.007mol) is dissolved in 25mL water, then is added dropwise in 4 solution, is generated
CdS；
(3) continue stirring 2 days；
(4) it centrifuges, extraction lower layer solid is washed 3-5 times, dry, N2Under atmosphere (flow 0.5mL/min), 400 DEG C of roastings
It burns 4 hours, obtains CdS.
Embodiment 5
0.5g graphite powders, 0.5g NaNO3, the dense H of 23mL2SO4It sequentially adds into 250mL round-bottomed flasks, and in ice bath
Stirring, is slowly added to 3g KMnO4After mixing, 35 DEG C of stirred in water bath 2 hours.Then, it is slowly added to the water of 40mL,
Temperature is increased to 95 DEG C, stirs 30min.Finally, it is slowly added to 100mL water, adds 3mL H2O2(30%), it filters, uses successively
1M hydrochloric acid, water washing are secondary, and filtrate is dried in vacuo at 50 DEG C and obtains graphene oxide (GO).
0.1g graphene oxides are added in the water of 200mL, ultrasonic 2h, be then added 100 μ L hydrazine hydrates (80%) with
1.4mL concentrated ammonia liquors (28%), by the solution, heating stirring 1 hour, then water washing filter, finally at 60 DEG C at 95 DEG C
Vacuum drying obtains redox graphene (RGO).
Embodiment 6
(1) 0.037g redox graphenes and the mixing of 15mL water, ultrasonication 30min；
(2) 1.6g CdCl are weighed2·2.5H2O (0.007mol) is added in above-mentioned solution, stirs 30min；
(3) 1.7g Na are weighed2S·9H2O (0.007mol) is dissolved in 25mL water, then is added dropwise to the solution of step (2)
In, generate CdS；
(6) continue stirring 2 days；
(7) it centrifuges, extraction lower layer solid is washed 3-5 times, dry, N2Under atmosphere (flow 0.5mL/min), 400 DEG C of roastings
It burns 4 hours, obtains RGO-CdS.
Embodiment 7
(1)0.2g TiO2(being purchased from Sinopharm Chemical Reagent Co., Ltd.) and 10mL water mix, ultrasonication 30min；
(2) 1.6g CdCl are weighed2·2.5H2O (0.007mol) is added in above-mentioned solution, stirs 30min；
(3) 1.7g Na are weighed2S·9H2O (.007mol) is dissolved in 25mL water, then is added dropwise to the solution of step (2)
In, generate CdS；
(4) continue stirring 2 days；
(5) it centrifuges, extraction lower layer solid is washed 3-5 times, dry, N2Under atmosphere (flow 0.5mL/min), 400 DEG C of roastings
It burns 4 hours, obtains TiO2-CdS。
Embodiment 8
(1)0.2g TiO2(being purchased from Sinopharm Chemical Reagent Co., Ltd.) and 10mL water mix, ultrasonication 30min；
(2) 0.037g redox graphenes and the mixing of 15mL water, ultrasonication 30min；
(3) two kinds of solution mixing, ultrasonication 30min；
(4) continue stirring 2 days；
(5) it centrifuges, extraction lower layer solid is washed 3-5 times, dry, N2Under atmosphere (flow 0.5mL/min), 400 DEG C of roastings
It burns 4 hours, obtains TiO2-RGO。
Embodiment 9
(1)0.2g TiO2(being purchased from Sinopharm Chemical Reagent Co., Ltd.) and 10mL water mix, ultrasonication 30min；
(2) 0.037g graphite powders and the mixing of 15mL water, ultrasonication 30min；
(3) two kinds of solution mixing, ultrasonication 30min；
(4) continue stirring 2 days；
(5) it centrifuges, extraction lower layer solid is washed 3-5 times, dry, N2Under atmosphere (flow 0.5mL/min), 400 DEG C of roastings
It burns 4 hours, obtains TiO2-C。
Substance made from above example is numbered, respectively：①TiO2(it is limited to be purchased from Chinese medicines group chemical reagent
Company), 2. RGO (embodiment 5), 3. CdS (embodiment 4), 4. TiO2- CdS (embodiment 7), 5. TiO2- RGO-CdS (embodiments
1), 6. RGO-CdS (embodiment 6), 7. TiO2- C (embodiment 9), 8. TiO2- RGO (embodiment 8), wherein RGO represents oxygen reduction
Graphite alkene, C represent graphite (being purchased from Sinopharm Chemical Reagent Co., Ltd.).
10 bacteriostatic experiment of embodiment
The method that actication of culture uses inclined-plane culture, fungi PDA culture medium, 28 DEG C of culture 2d；Bacterium beef extract-peptone
37 DEG C of culture 16h of culture；8 kinds of composite titania materials observe inhibition zone by Odontothrips loti.
As Figure 1-Figure 4, only numbering 3.-material 6. has fungistatic effect.
Embodiment 11
The different materials 0.5ml of antibacterial effect is taken to be added conical flask (fluid nutrient medium for being connected to strain) respectively, 37 DEG C
Shaken cultivation 12h calculates bacteriostasis rate using gradient dilution method, and bacteriostasis rate (%)=[(control group-experimental group)/control group] ×
100%.
1 Escherichia coli bacteriostasis rate Experiment Data Records table of table
2 staphylococcus aureus bacteriostasis rate Experiment Data Records table of table
As can be seen from Table 1 and Table 2, either to Escherichia coli or staphylococcus aureus, titanium dioxide composite wood
Bacteriostasis rate highest is all 5. number sample in material, to large intestine bacteriostasis rate up to 80.5%, to golden Portugal's bacteriostasis rate up to 87.4%.5. it is anti-
For bacterium effect than good anti-bacterial effect 4., can obtain redox graphene can improve the antibacterial ability of titanium dioxide.This is because leading
Electrical good redox graphene can promote the transmission of light induced electron, reduce the recombination probability of light induced electron and hole, into
And improve the bacteriostasis rate of composite material.
Fig. 5 and Fig. 6 is TiO respectively2- RGO-CdS composite materials act on before and after Escherichia coli and staphylococcus aureus
SEM schemes.The result shows that the preceding bacterium length of effect is full, surface is smooth, it is seen that its vigorous growing power, Escherichia coli after effect
Surface irregularity, some areas are gradually recessed atrophy, may be dissolved inside bacterium, and it is smaller to grow head, withers and cuddles up in a heap
Until dead.
The antimicrobial mechanism of composite titania material may be it can quickly and effectively decompose constitute bacterium organic matter and
Bacterium, which is rely, generates the organic nutrient substance of breeding, inhibits growth；Photocatalysis generates OH and O2 -Microorganism can be bombarded, damage is thin
Born of the same parents' structure makes bacterium surface generation cavity make the slow leakage of RNA and protein to kill bacterium.It is observed in electron microscope thin
Bacterium adsorption impurity, head is small, there is atrophy, dissolving sign.Simple apparent observation only has been carried out to its mechanism herein and has been pushed away
It surveys, to obtain definite Antibacterial Mechanism, it is also necessary to further research.
Embodiment 12
1, by with antibacterial ability composite material and paint according to mass ratio 1:30 are mixed, and are coated after stirring evenly
On aluminium sheet, antibacterial coated plate is obtained after 180 DEG C of drying, carries out antibacterial experiment；
2, the antibacterial of above-mentioned antibacterial coated plate surface layer coating is ground into except formaldehyde composite material and paint are scraped off with blade
Powder carries out antibacterial experiment.
Significantly inhibit black from figure 7 it can be seen that being coated with and having around the aluminium sheet of recovery condensation material and paint mixture
Aspergillus growth inhibition zone (a), without apply photochemical catalyst aluminium sheet around overgrow with aspergillus niger (b).The result shows that compound
It is coated on aluminium sheet after material and paint mixing, it is same to have the function of apparent anti-black-koji mould.
As can be seen from Figure 8, around the powder (b) after simple composite material (a) and paint and composite material mixing are dried
Inhibit the inhibition zone of rhizopus growth with apparent, and overgrows with rhizopus around blank sample (c).The result shows that multiple
Powder after condensation material, paint and composite material mixing drying all has good inhibiting effect to rhizopus growth.
Embodiment 13
(1) coating of embodiment 12 is coated in 30cm2Aluminium sheet on, dry obtained test sample, totally 15 pieces.
(2) 2 glass bars for winding the gauze that is of five storeys uprightly are put into the reagent bottle of 2 500mL, are respectively charged into 200mL
Pollutant (formaldehyde 0.2%), mark A1, A2.
(3) 15 pieces of test samples are laid in experimental cabin B.
(4) source of release A1, A2 are respectively put into blank test cabin A and sampling test cabin B, close hatch door immediately.
(5) A cabin (1.5m are opened3) and the cabins B (1.5m3) fan stir 1min, close fan, sampling determination blank cabin A's
Primary pollutant concentration.
(6) experimentation opens fluorescent lamp.After for 24 hours, test analysis, concentration are acquired to the air in the cabins A and the cabins B respectively
It is C respectivelyAAnd CB。
The removal rate of pollutant is calculated as follows：
Y (%)=(CA-CB)/CA× 100%
Testing result is as follows：
The present invention also goes formaldehyde efficiency to be tested in three kinds of composite materials of embodiment 1-3 simultaneously, as a result such as Fig. 9
Shown, for redox graphene concentration when 5%, antibacterial goes formaldehyde efficiency highest except formaldehyde composite material.Meanwhile from
Fig. 9 it is found that the addition of redox graphene can effectively be promoted composite titania material remove formaldehyde efficiency.This is because leading
Electrical good redox graphene can promote the transmission of light induced electron, reduce the recombination probability of light induced electron and hole, together
The efficiency that composite material removes formaldehyde can be improved in sample.
The present invention has also investigated calcination atmosphere and calcination temperature to the antibacterial of embodiment 1 except formaldehyde composite material removes formaldehyde
The influence of efficiency, as a result as shown in Figure 10 and Figure 11, discovery roast manufactured antibacterial with nitrogen atmosphere and remove formaldehyde composite material
It goes formaldehyde efficiency to be higher than the antibacterial made of air roasting and removes formaldehyde composite material.This is because under oxygen roasting condition, also
Former graphene oxide is equal to the composite material for not adding redox graphene by the dioxygen oxidation burn off in air.And
It is roasted under nitrogen protection, redox graphene will not can be promoted the transmission of light induced electron, be subtracted by burn off, redox graphene
The recombination probability of few light induced electron and hole, therefore show higher except formaldehyde efficiency.In addition, 400 DEG C of calcination temperature is better than 300
℃。
Claims (1)
1. a kind of coating, which is characterized in that remove formaldehyde composite material and paint comprising titanium dioxide antibiotic, titanium dioxide antibiotic removes
The mass ratio of formaldehyde composite material and paint is 1:30；
The titanium dioxide antibiotic is except the preparation method of formaldehyde composite material：
(1)0.2g TiO2It is mixed with 10mL water, ultrasonication 30min；
(2) 0.064g redox graphenes and the mixing of 15mL water, ultrasonication 30min；
(3) above two solution is mixed, ultrasonication 30min；
(4) 1.6g CdCl are weighed2·2.5H2O is added in the mixed solution of step (3), stirs 30min；
(5) 1.7g Na are weighed2S·9H2O is dissolved in 25mL water, then is added dropwise in the solution of step (4), and CdS is generated；
(6) continue stirring 2 days；
(7) it centrifuges, extraction lower layer solid is washed 3-5 times, and dry, flow is the N of 0.5mL/min2Under atmosphere, 400 DEG C of roastings 4 are small
When, it obtains titanium dioxide antibiotic and removes formaldehyde composite material.
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| CN110373891A (en) * | 2019-07-16 | 2019-10-25 | 东华大学 | Load bismuth tungstate/visible light-responded composite antibacterial fabric of titanium dioxide/redox graphene and preparation method thereof |
| CN110352983A (en) * | 2019-07-16 | 2019-10-22 | 东华大学 | Redox graphene loads bismuth tungstate/titanium dioxide composite visible light catalyst anti-biotic material and preparation method thereof |
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| CN101153149A (en) * | 2006-09-25 | 2008-04-02 | 天津市振东涂料有限公司 | Method of producing ultra-bright light catalysis degradation antimicrobial environment protection paint |
| CN102861600A (en) * | 2012-10-10 | 2013-01-09 | 江苏大学 | Graphene oxide/silver phosphate/P25 composite material and preparation method thereof |
| CN103357424A (en) * | 2013-07-26 | 2013-10-23 | 福州大学 | Photocatalyst for selective oxidation of toluene and toluene derivatives |
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| CN101153149A (en) * | 2006-09-25 | 2008-04-02 | 天津市振东涂料有限公司 | Method of producing ultra-bright light catalysis degradation antimicrobial environment protection paint |
| CN102861600A (en) * | 2012-10-10 | 2013-01-09 | 江苏大学 | Graphene oxide/silver phosphate/P25 composite material and preparation method thereof |
| CN103357424A (en) * | 2013-07-26 | 2013-10-23 | 福州大学 | Photocatalyst for selective oxidation of toluene and toluene derivatives |
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