CN104001537B - Improve the method for TiO2/ diatomite composite material visible light catalysis activity and anti-microbial property - Google Patents
Improve the method for TiO2/ diatomite composite material visible light catalysis activity and anti-microbial property Download PDFInfo
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- CN104001537B CN104001537B CN201410270737.5A CN201410270737A CN104001537B CN 104001537 B CN104001537 B CN 104001537B CN 201410270737 A CN201410270737 A CN 201410270737A CN 104001537 B CN104001537 B CN 104001537B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 30
- 230000000694 effects Effects 0.000 title claims abstract description 30
- 230000000845 anti-microbial effect Effects 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 38
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004202 carbamide Substances 0.000 claims abstract description 22
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 21
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052709 silver Inorganic materials 0.000 claims abstract description 18
- 239000004332 silver Substances 0.000 claims abstract description 18
- 238000007598 dipping method Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 101710134784 Agnoprotein Proteins 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000002835 absorbance Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 230000001737 promoting effect Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 12
- 239000000047 product Substances 0.000 abstract description 12
- 238000005470 impregnation Methods 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 239000013066 combination product Substances 0.000 abstract description 2
- 229940127555 combination product Drugs 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- -1 wallpaper Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
The present invention relates to and improve TiO
2the method of/diatomite composite material visible light catalysis activity and anti-microbial property.The method is by the TiO of preparation
2/ diatomite composite material is at certain density urea (CO (NH
2)
2) and silver nitrate (AgNO
3) stir dipping in solution, by sample drying after impregnation certain hour, obtain TiO
2/ diatomite composite material dipping urea, silver nitrate combination product; This impregnation product is calcined at a certain temperature, breaks up depolymerization after cooling, namely obtain the N-TiO with visible light catalysis activity and anti-microbial property
2/ diatomite carries silver composite material.This method adopts the method for direct impregnation in urea and liquor argenti nitratis ophthalmicus, whole process is added without other reagent, avoid in preparation process and produce a large amount of waste water, there is easy, efficient, clean advantage, and composite has wider visible light-responded scope and anti-microbial property.The N-TiO of prepared by the present invention have visible light catalysis activity and anti-microbial property
2/ diatomite carries silver composite material and can be used for indoor environmental pollution purification techniques field.
Description
Technical field
The present invention relates to and improve TiO
2the method of/diatomite composite material visible light catalysis activity and anti-microbial property, belongs to nonmetallic mineral material preparation, environmental pollution purification techniques field.
Background technology
TiO
2as a kind of catalysis material of efficient, nontoxic and stable chemical nature, under UV-irradiation, the common contaminant such as toluene, phenol, formaldehyde and dyestuff, can at TiO
2the catalyzed degraded in surface.For improving TiO
2photocatalytic activity, usual TiO
2expect to be made into ultra-fine, nano particle, but ultra-fine, nano-TiO
2complicated process of preparation, and there is the shortcoming of easily reuniting, reclaiming difficulty in actual use.In recent years, the carriers such as diatomite, active carbon, silica gel, zeolite, bentonite, glass and nickel foam are adopted to fix TiO
2, can disperse preferably and reclaim ultra-fine, nano-TiO
2, become TiO
2composite photocatalyst material study hotspot.
Diatomite is a kind of natural porous nonmetallic mineral material, has that specific surface is large, a feature of the strong and stable in properties of adsorptivity, about TiO
2the preparation technology of/diatomite composite material, existing a lot of pertinent literature report, mainly adopts diatomite to make carrier, by technical process such as hydrolysis methods, sol-gal process and hydro-thermal methods, by TiO
2be fixed on diatomite for the preparation of TiO with the form of hydrated titanium dioxide, titanium hydroxide
2/ diatomite composite material, is shown in below with reference to document: 1. Chinese invention patent " take super-cell as the loaded nano TiO of carrier
2the preparation method of catalysis material ", application number: CN200910235208.0, applicant: China Mining Univ. (Beijing); 2. Wang Lijian etc., the preparation of Titania/diatomite Composite, silicate journal, 2006,34 (7); 3. " a kind of sol-gel process prepares TiO to Chinese invention patent
2the method of/diatomite composite photocatalytic material ", application number: CN201310117399.7, applicant: Kunming University of Science and Technology; 4. side cultivates, and hydro-thermal method prepares TiO
2-diatomite composite material and photocatalysis performance thereof, functional material and device journal, 2010,16 (1).Based on TiO
2the strong absorption of/diatomite composite material and Photocatalytic Degradation Property, now by its Application and Development in the environmental friendly indoor building materials such as wallpaper, coating, shutter and timber floor, the common volatile harmful gas such as toluene, formaldehyde of degraded indoor environment.But, TiO
2there is higher energy gap, Detitanium-ore-type TiO
2energy gap be 3.2eV, absorbing wavelength can only be less than the ultraviolet light of 390nm, and ultraviolet light proportion in sunshine very little (being less than 5%), for utilizing indoor light source and sunshine preferably, exploitation has the TiO of visible light catalysis activity
2/ diatomite composite material is significant.
In recent years, people adopt various method of modifying, as element (metal, nonmetal, rare earth) doping, semiconductors coupling, dye sensitization etc. are attempted to improve TiO
2visible light catalysis activity, wherein N element doped Ti O
2show excellent photocatalysis performance, have good application potential.Find through searching document, 5. Chinese invention patent name is called " a kind of tripolite loading nitrogen-doped nanometer TiO
2the preparation method of catalysis material ", application number is: CN201210205768.3, which discloses one and carry out high-temperature heat treatment in nitrogen, prepare tripolite loading nitrogen-doped nanometer TiO
2the method of catalysis material, there is the shortcoming that nitrogen circulation consumption is large, equipment requirement is high in the method; 6. Chinese invention patent name is called that " a kind of take diatomite as the visible light-responded TiO of matrix
2the preparation method of mixed crystal ", application number is: CN200810156050.3, which discloses a kind of employing and prepares TiO
2mixed crystal improves with TiO
2-diatomaceous visible light-responded, do not relate to element doping.In addition, because indoor are main life, the workplace of the mankind, along with the daily life activity of the mankind, inevitably produce some bacteriums, harm humans is healthy, and metal element A g, Cu, Zn etc. show anti-microbial property, wherein the anti-microbial property of Ag is the most outstanding, and silver can at TiO
2surface can form active sites, is conducive to stoping TiO
2the compound in surface light induced electron and hole, improves TiO greatly
2photocatalytic activity, 7. Chinese invention patent name is called " method of Diatomite-based Porous Ceramics and loading Ag doped with nano TiO 2 thereof ", application number is: CN201010216099.0, which disclose one to be decomposed by ultraviolet catalytic silver nitrate, carry out the method for loading Ag doped with nano TiO 2, there is silver carrying amount and be difficult to control, easily cause the loss of noble silver, influence factor many and be difficult to realize the shortcoming of suitability for industrialized production in the method, and this product visible light catalysis activity is more weak.
For current TiO
2low and the shortcoming of antibacterial effect difference of/diatomite composite material visible light catalysis activity, the invention provides and improve TiO
2the method of/diatomite composite material visible light catalysis activity and anti-microbial property.
Summary of the invention
Technical scheme of the present invention is: by the TiO of preparation
2/ diatomite composite material is at pre-configured certain density urea (CO (NH
2)
2) and silver nitrate (AgNO
3) carry out stirring dipping in solution, after impregnation certain hour, sample is carried out drying, obtain TiO
2/ diatomite composite material dipping urea, silver nitrate combination product; This impregnation product is calcined at a certain temperature, breaks up depolymerization after calcined product cooling, namely obtain the N-TiO with visible light catalysis activity and anti-microbial property
2/ diatomite carries silver composite material product.
Its processing step is as follows:
(1) by TiO
2/ diatomite composite material: urea: the quality proportioning of silver nitrate is 1:(0.08 ~ 1): (0.001 ~ 0.04), takes a certain amount of TiO
2/ diatomite composite material, urea (CO (NH
2)
2) and silver nitrate (AgNO
3), urea and silver nitrate are dissolved in the aqueous solution that clear water is made into urea and silver nitrate mass concentration 10% ~ 30%;
(2) by TiO
2/ diatomite composite material is scattered in the mixed solution of urea and silver nitrate, stirs dipping 0.5 ~ 2h under normal temperature;
(3) sample after dipping is transferred in evaporimeter or freeze-dryer, at 50 ~ 90 DEG C dry or-10 ~-30 DEG C at freeze drying;
(4) desciccate is placed in calcining furnace, at 350 ~ 550 DEG C of temperature, calcining 1 ~ 5h;
(5) break up depolymerization after calcined product being cooled to room temperature, namely obtain the N-TiO with visible light catalysis activity and anti-microbial property
2/ diatomite carries silver composite material.
The prepared N-TiO with visible light catalysis activity and anti-microbial property
2/ diatomite carries silver composite material and can be used for the contaminative VOCs such as indoor formaldehyde, toluene and benzene degraded and anti-bacteria grows.
This method adopts the method for direct impregnation load in urea and liquor argenti nitratis ophthalmicus, whole process is added without other reagent, avoid in preparation process and produce a large amount of waste water, there is easy, efficient, clean advantage, and composite has wider visible light-responded scope and anti-microbial property.The N-TiO of prepared by the present invention have visible light catalysis activity and anti-microbial property
2/ diatomite carries silver composite material and can be used for indoor environmental pollution purification techniques field.
Accompanying drawing explanation
Fig. 1 is the N-TiO with visible light catalysis activity and anti-microbial property prepared by the specific embodiment of the invention one
2/ diatomite carries silver composite material and TiO
2ultraviolet-visible absorption spectroscopy (UV-Vis) comparison diagram of/diatomite composite material, N-TiO of the present invention
2/ diatomite carries silver composite material comparatively general T iO within the scope of visible ray 390 ~ 500nm
2/ diatomite composite material absorbance significantly promotes, and shows obvious visible light catalysis activity.
Fig. 2 is the N-TiO with visible light catalysis activity and anti-microbial property prepared by the specific embodiment of the invention one
2/ diatomite carries the TEM figure of silver composite material.
Detailed description of the invention
Embodiment one: (1) takes TiO respectively
2/ diatomite composite material 10g, urea 3g, silver nitrate 0.01g, and urea and silver nitrate to be dissolved in 10ml water to obtain solution A, then by TiO
2/ diatomite composite material is scattered in solution A, is placed in normal temperature and stirs dipping 0.5h.
(2) sample after dipping is transferred in rotary evaporator, at 70 DEG C of Rotary dryings.
(3) dried sample is placed in calcining furnace, at 400 DEG C of temperature, calcining 2h.Calcined product is cooled to room temperature, after being ground into powder, namely obtains the N-TiO with visible light catalysis activity and anti-microbial property
2/ diatomite carries silver composite material product.
Embodiment two: (1) takes TiO respectively
2/ diatomite composite material 10g, urea 2g, silver nitrate 0.05g, and urea and silver nitrate to be dissolved in 10ml water to obtain solution B, then by TiO
2/ diatomite composite material is scattered in solution B, is placed in normal temperature and stirs dipping 1h.
(2) sample after dipping is transferred in rotary evaporator, at 75 DEG C of Rotary dryings.
(3) dried sample is placed in calcining kiln, at 450 DEG C of temperature, calcining 3h.Calcined product is cooled to room temperature, after breaing up, namely obtains the N-TiO with visible light catalysis activity and anti-microbial property
2/ diatomite carries silver composite material product.
Embodiment three: (1) takes TiO respectively
2/ diatomite composite material 10g, urea 4g, silver nitrate 0.15g, and urea and silver nitrate to be dissolved in 25ml water to obtain solution C, then by TiO
2/ diatomite composite material is scattered in solution C, is placed in normal temperature and stirs dipping 1h.
(2) sample after dipping is transferred in freeze-dryer, freeze drying.
(3) dried sample is placed in calcining kiln, at 420 DEG C of temperature, calcining 5h.Calcined product is cooled to room temperature, after breaing up, namely obtains the N-TiO with visible light catalysis activity and anti-microbial property
2/ diatomite carries silver composite material product.
Effect is tested: (1) visible light catalysis activity is tested: at 1m
3environmental chamber in regulate initial concentration of formaldehyde to be 10mg/m
3, take the N-TiO with visible light catalysis activity and anti-microbial property prepared in 10g embodiment
2/ diatomite carries silver composite material and is evenly coated on glass plate, adopts 20W daylight lamp as light source Continuous irradiation 48h, carries out formaldehyde degradation by photocatalytic oxidation process experiment, and carry out general T iO under the same conditions
2/ diatomite composite material contrast experiment, experimental result is as shown in table 1.
(2) anti-microbial property experiment: reference " nano inorganic material anti-microbial property detection method " (GB/T21510-2008) take staphylococcus aureus as experimental strain, adopts the anti-microbial property of colony counting method test sample, tests general T iO respectively
2the N-TiO with visible light catalysis activity and anti-microbial property prepared in/diatomite composite material and embodiment
2/ diatomite carries the anti-microbial property of silver composite material, and experimental result is as shown in table 1.
The detection analysis result of table 1 embodiment sample
Claims (1)
1. improve TiO
2the method of/diatomite composite material visible light catalysis activity and anti-microbial property, it is characterized in that significantly promoting the absorbance of composite within the scope of visible ray 390 ~ 500nm, and have anti-microbial property, its processing step is as follows:
(1) by TiO
2/ diatomite composite material: urea: the quality proportioning of silver nitrate is 1:(0.08 ~ 1): (0.001 ~ 0.04), takes a certain amount of TiO
2/ diatomite composite material, urea (CO (NH
2)
2) and silver nitrate (AgNO
3), urea and silver nitrate are dissolved in the aqueous solution that clear water is made into urea and silver nitrate mass concentration 10% ~ 30%;
(2) by TiO
2/ diatomite composite material is scattered in the mixed solution of urea and silver nitrate, stirs dipping 0.5 ~ 2h under normal temperature;
(3) sample after dipping is transferred in evaporimeter or freeze-dryer, at 50 ~ 90 DEG C dry or-10 ~-30 DEG C at freeze drying;
(4) desciccate is placed in calcining furnace, at 350 ~ 550 DEG C of temperature, calcining 1 ~ 5h;
(5) break up depolymerization after calcined product being cooled to room temperature, namely obtain the N-TiO with visible light catalysis activity and anti-microbial property
2/ diatomite carries silver composite material.
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|---|---|---|---|
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|---|---|---|---|
| CN201410270737.5A CN104001537B (en) | 2014-06-18 | 2014-06-18 | Improve the method for TiO2/ diatomite composite material visible light catalysis activity and anti-microbial property |
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| CN106334396A (en) * | 2016-09-24 | 2017-01-18 | 上海大学 | Method capable of inhibiting formation of NBaP in atmospheric particulates |
| CN106984306B (en) * | 2017-04-28 | 2019-08-06 | 成都理工大学 | One kind having antibacterial and the difunctional surrounding purifying material of photocatalysis and preparation method thereof |
| CN107162546A (en) * | 2017-07-13 | 2017-09-15 | 江苏新大乘环保科技有限公司 | A kind of diatom plate with antibacterial functions and preparation method thereof |
| CN108244145A (en) * | 2018-02-07 | 2018-07-06 | 广州市凯卫莎环保科技有限公司 | Triple effect all-weather light catalyst indoor air purification agent and preparation method and application |
| CN108940339A (en) * | 2018-07-12 | 2018-12-07 | 浙江正洁环境科技有限公司 | A kind of N-TiO2/ calcium system bentonite composite adsorption catalyst and application |
| CN109046340B (en) * | 2018-08-21 | 2021-09-24 | 中科广化（重庆）新材料研究院有限公司 | Surface-modified visible light catalytic material and preparation method and application thereof |
| CN109806765B (en) * | 2019-03-26 | 2021-12-07 | 中国建筑材料科学研究总院有限公司 | Air purification composite material and preparation method thereof |
| CN111974156A (en) * | 2019-05-24 | 2020-11-24 | 宁夏大学 | Preparation method of scavenger for efficiently degrading gaseous pollutants |
| CN113383793B (en) * | 2021-07-15 | 2022-07-19 | 曲靖师范学院 | Cu/TiO2/diatom ooze composite antibacterial material, preparation method and application thereof |
| CN115039791A (en) * | 2022-07-13 | 2022-09-13 | 塔里木大学 | Vermiculite antibacterial functional material and preparation method thereof |
| CN116237045A (en) * | 2023-02-10 | 2023-06-09 | 山东凯大新型材料科技有限公司 | Preparation method and application of diatomite-based photo-thermal catalytic composite material |
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