CN107519856A - A kind of redox graphene/TiO2The preparation and application of composite photocatalyst material - Google Patents
A kind of redox graphene/TiO2The preparation and application of composite photocatalyst material Download PDFInfo
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- CN107519856A CN107519856A CN201710825844.3A CN201710825844A CN107519856A CN 107519856 A CN107519856 A CN 107519856A CN 201710825844 A CN201710825844 A CN 201710825844A CN 107519856 A CN107519856 A CN 107519856A
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- photocatalyst material
- composite photocatalyst
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 37
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000015556 catabolic process Effects 0.000 claims abstract description 13
- 238000006731 degradation reaction Methods 0.000 claims abstract description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims abstract description 12
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 229930040373 Paraformaldehyde Natural products 0.000 abstract description 6
- 229920002866 paraformaldehyde Polymers 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 238000005286 illumination Methods 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000011521 glass Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000003556 assay Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- SBHHFAIXPSFQLT-UHFFFAOYSA-N methylidene(oxido)oxidanium Chemical compound [O-][O+]=C SBHHFAIXPSFQLT-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/70—Non-metallic catalysts, additives or dopants
- B01D2255/702—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
Abstract
The invention belongs to nano composite material and photocatalysis field, is more particularly to a kind of redox graphene/TiO2The preparation of composite photocatalyst material and its application in formaldehyde degradation by photocatalytic oxidation process.Using simple hydrothermal synthesis method, for the graphene oxide prepared using cheap titanyl sulfate and Hummers methods as raw material, the mixed liquor of water and ethanol is solvent, and graphene oxide/TiO of even structure is can obtain in the presence of concentrated hydrochloric acid2Composite Nano catalysis material.The present invention is not only simple to operate, and cost is low, can largely synthesize graphene oxide/TiO2Composite, and titanium dioxide is in anatase crystal in the composite prepared, and the stability of material is good, stable performance, and photocatalytic activity is high, and under visible light illumination, PARA FORMALDEHYDE PRILLS(91,95) has very high degradation rate.
Description
Technical field
The invention belongs to nano composite material and photocatalysis field, is more particularly to a kind of redox graphene/TiO2
The preparation of composite photocatalyst material and its application in formaldehyde degradation by photocatalytic oxidation process.
Background technology
Formaldehyde pollution in indoor environment, to the very harmful of human body.At present, researcher is more by the way of absorption and catalysis
Reduce the formaldehyde in indoor environment.Redox graphene is a kind of derivative of graphene, it may have unique two-dimensional structure,
Larger specific surface area, which becomes, prepares the ideal carrier of load-type composite material, and redox graphene can increase by two
Catalysis utilization rate of the titanium oxide to visible light wave.
Titanium dioxide has larger specific surface area, the special construction and self-dispersing on surface, and wherein Detitanium-ore-type light is urged
Change active highest, but it is relatively low to the visible light utilization efficiency in natural light, so cause its application in photocatalysis field by
Limit.
Therefore, it is how simply and effectively that it is compound with graphene oxide progress, and then give full play to composite
Synergy between the two prepares the more excellent composite nano materials of performance, has in catalytic degradation indoor environment volatility
There is very important Research Significance in machine thing.
The content of the invention
It is an object of the invention to provide a kind of redox graphene/TiO2The preparation and application of composite photocatalyst material,
Not only easy to operate, cost is low, and can largely synthesize redox graphene/TiO2Composite, and prepare
Titanium dioxide is anatase crystal in composite, and composite specific surface area is big, and catalytic activity is high, under visible light conditions,
PARA FORMALDEHYDE PRILLS(91,95) has very high degradation rate.
In order to solve the above problems, the technical scheme is that：
A kind of redox graphene/TiO2The preparation method of composite photocatalyst material, including following steps：
(1) graphene oxide is prepared using Hummers methods；
(2) graphene oxide powder prepared by step (1) is scattered in water/alcohol mixeding liquid, the volume of water and ethanol
Than 1:1, ultrasonic disperse is uniform, obtains the uniform dispersion that mass concentration is 2~9 ‰ graphene oxides；To graphene oxide point
The concentrated hydrochloric acid of addition cetyl trimethylammonium bromide surfactant and mass fraction 30~40% in dispersion liquid, 20~40 DEG C
Under the conditions of stir 1~2h, then add titanyl sulfate, continue 1~2h of stirring；
(3) mixed liquor of step (2) is placed in the autoclave interior sealing with polytetrafluoroethyllining lining, hydro-thermal reaction 12
~24h, room temperature is naturally cooled to after reaction completely, respectively with deionized water and absolute ethyl alcohol filtering and washing to pH=7, last 40
Vacuum drying under the conditions of~80 DEG C, produce redox graphene/TiO2Composite photocatalyst material.
Described redox graphene/TiO2The preparation method of composite photocatalyst material, by Hummers methods to raw material
Control, make graphene oxide size be 0.1~50 μm.
Described redox graphene/TiO2The preparation method of composite photocatalyst material, graphene oxide, cetyl
The mass ratio of trimethylammonium bromide, concentrated hydrochloric acid and titanyl sulfate is：1:11:6~12:10~150.
Described redox graphene/TiO2The preparation method of composite photocatalyst material, it is preferred that graphene oxide,
The mass ratio of cetyl trimethylammonium bromide, concentrated hydrochloric acid and titanyl sulfate is：1:11:8.6:30~100.
Described redox graphene/TiO2The preparation method of composite photocatalyst material, titanium dioxide are brilliant in anatase
Type, the temperature of hydro-thermal reaction is 100~180 DEG C.
Described redox graphene/TiO2The preparation method of composite photocatalyst material, in composite photocatalyst material, also
The mass ratio of former graphene oxide/titanium dioxide is 1：10~200.
Described redox graphene/TiO2The application of composite photocatalyst material, obtained redox graphene/
TiO2Composite is used for degradation of formaldehyde.
The present invention design philosophy be：
The graphene oxide that the present invention is prepared using cheap titanyl sulfate and Hummers methods as primary raw material, water/
In the homogeneous system of ethanol, adding CTAB makes graphene oxide disperse evenly in homogeneous system, and then titanyl sulfate exists
Under conditions of concentrated hydrochloric acid, generation TiO is hydrolyzed by water-heat process2, and the surface of graphene oxide of reduction is dispersed in, and
Agglomeration does not occur, adjusts the energy gap of titanium dioxide, increases its range of receiving to visible ray, in radiation of visible light
Under, the degradation rate of PARA FORMALDEHYDE PRILLS(91,95) reaches 90%.
Compared with prior art, advantages of the present invention and beneficial effect are：
The inventive method technique is simple, and reaction condition is gentle, raw material asepsis environment-protecting used, is prepared with simple method
Go out degradable formaldehyde oxide of high activity graphene/TiO of favorable dispersibility2Composite,
Embodiment
Only enumerating preferable specific embodiment below, the present invention will be described, it is necessary to it is pointed out here that be in detail below
Embodiment is served only for that the invention will be further described, does not represent limiting the scope of the invention.The present invention is not being departed from
On the premise of principle, any modification, equivalent substitution or improvement for being made within the spirit and principles of the invention etc., it all should wrap
It is contained within protection scope of the present invention.
Embodiment 1
In the present embodiment, redox graphene/TiO2The preparation method of composite photocatalyst material, is comprised the following steps that：
(1) 50mg Hummers methods are weighed and prepare graphene oxide powder, are dissolved in water/ethanol (volume ratio 1:1) mixing
In liquid, ultrasonic disperse, the uniform dispersion that graphene oxide mass concentration is 2 ‰ is obtained；
(2) 550mg cetyl trimethylammonium bromide (CTAB), stirring are added into above-mentioned graphene oxide dispersion
Uniformly, the concentrated hydrochloric acid that 2mL mass fractions are 35% is added, 2h is stirred at 30 DEG C；
(3) weigh in mixed liquor of the 1.5g titanyl sulfate in above-mentioned (2), continue to stir 2h at 30 DEG C；
(4) mixed liquor for obtaining above-mentioned (3) is moved into in polytetrafluoroethyllining lining autoclave, is sealed, 120
Under the conditions of DEG C, hydro-thermal reaction 20h, reaction naturally cools to room temperature after terminating, and is filtered wash with deionized water and absolute ethyl alcohol respectively
Wash to pH=7, finally the vacuum drying 12h under the conditions of 40 DEG C, produces graphene oxide/TiO2Composite photocatalyst material.
(5) by obtained graphene oxide/TiO2Composite photocatalyst material is used for the assay method of degradation of formaldehyde：Take formaldehyde
Solution 0.02mol/L, insert volatilization gas and received in storehouse, 25 DEG C of temperature in cabin；Open visible ray and circulated air, light source 50
Individual wavelength is 458nm blue LED.Redox graphene/TiO2Catalyst is equably coated in square glass with water
Drying is placed in diode top on glass piece, and reactor is closed container.Different bars are determined using formaldehyde gas detector respectively
The change in concentration of formaldehyde under part.Graphene oxide/the TiO prepared after tested2Composite photocatalyst material is in radiation of visible light condition
Under, the degradation rates of 24 hours PARA FORMALDEHYDE PRILLS(91,95)s is up to 92%, and stable performance.
Embodiment 2
In the present embodiment, redox graphene/TiO2The preparation method of composite photocatalyst material, is comprised the following steps that：
(1) 50mg Hummers methods are weighed and prepare graphene oxide powder, are dissolved in water/ethanol (volume ratio 1:1) mixing
In liquid, ultrasonic disperse, the uniform dispersion that graphene oxide mass concentration is 2 ‰ is obtained；
(2) 550mg cetyl trimethylammonium bromide (CTAB), stirring are added into above-mentioned graphene oxide dispersion
Uniformly, the concentrated hydrochloric acid that 1.5mL mass fractions are 35% is added, 2h is stirred at 30 DEG C；
(3) weigh in mixed liquor of the 2g titanyl sulfate in above-mentioned (2), continue to stir 2h at 30 DEG C；
(4) mixed liquor for obtaining above-mentioned (3) is moved into in polytetrafluoroethyllining lining autoclave, is sealed,
Under the conditions of 160 DEG C, hydro-thermal reaction 20h, reaction naturally cools to room temperature after terminating, and is filtered respectively with deionized water and absolute ethyl alcohol
Washing is to pH=7, and finally the vacuum drying 12h under the conditions of 40 DEG C, produces graphene oxide/TiO2Composite photocatalyst material.
(5) by obtained graphene oxide/TiO2Composite photocatalyst material is used for the assay method of degradation of formaldehyde：Take formaldehyde
Solution 0.02mol/L, insert volatilization gas and received in storehouse, 25 DEG C of temperature in cabin；Open visible ray and circulated air, light source 50
Individual wavelength is 458nm blue LED.Redox graphene/TiO2Catalyst is equably coated in square glass with water
Drying is placed in diode top on glass piece, and reactor is closed container.Different bars are determined using formaldehyde gas detector respectively
The change in concentration of formaldehyde under part.Graphene oxide/the TiO prepared after tested2Composite photocatalyst material is in radiation of visible light condition
Under, the degradation rates of 24 hours PARA FORMALDEHYDE PRILLS(91,95)s is up to 96%, and stable performance.
Embodiment result shows, the present invention uses simple hydrothermal synthesis method, with cheap titanyl sulfate and
Graphene oxide prepared by Hummers methods be raw material, and the mixed liquor of water and ethanol is solvent, available in the presence of concentrated hydrochloric acid
Graphene oxide/TiO of even structure2Composite Nano catalysis material.The present invention is not only simple to operate, and cost is low, Ke Yi great
Amount synthesis graphene oxide/TiO2Composite, and titanium dioxide is in anatase crystal in the composite prepared, the material
Stability is good, stable performance, and photocatalytic activity is high, and under visible light illumination, PARA FORMALDEHYDE PRILLS(91,95) has very high degradation rate.
Claims (7)
- A kind of 1. redox graphene/TiO2The preparation method of composite photocatalyst material, it is characterised in that including following Step：(1) graphene oxide is prepared using Hummers methods；(2) graphene oxide powder prepared by step (1) is scattered in water/alcohol mixeding liquid, the volume ratio 1 of water and ethanol: 1, ultrasonic disperse is uniform, obtains the uniform dispersion that mass concentration is 2~9 ‰ graphene oxides；To graphene oxide dispersion The middle concentrated hydrochloric acid for adding cetyl trimethylammonium bromide surfactant and mass fraction 30~40%, under the conditions of 20~40 DEG C 1~2h is stirred, titanyl sulfate is then added, continues 1~2h of stirring；(3) mixed liquor of step (2) is placed in the autoclave interior sealing with polytetrafluoroethyllining lining, hydro-thermal reaction 12~ 24h, room temperature is naturally cooled to after reaction completely, respectively with deionized water and absolute ethyl alcohol filtering and washing to pH=7, last 40~ Vacuum drying under the conditions of 80 DEG C, produce redox graphene/TiO2Composite photocatalyst material.
- 2. redox graphene/TiO as claimed in claim 12The preparation method of composite photocatalyst material, it is characterised in that By control of the Hummers methods to raw material, it is 0.1~50 μm to make graphene oxide size.
- 3. redox graphene/TiO as claimed in claim 12The preparation method of composite photocatalyst material, it is characterised in that Graphene oxide, cetyl trimethylammonium bromide, the mass ratio of concentrated hydrochloric acid and titanyl sulfate are：1:11:6~12:10~ 150。
- 4. redox graphene/TiO as claimed in claim 12The preparation method of composite photocatalyst material, it is characterised in that Preferably, the mass ratio of graphene oxide, cetyl trimethylammonium bromide, concentrated hydrochloric acid and titanyl sulfate is：1:11:8.6:30 ~100.
- 5. redox graphene/TiO as claimed in claim 12The preparation method of composite photocatalyst material, it is characterised in that Titanium dioxide is in anatase crystal, and the temperature of hydro-thermal reaction is 100~180 DEG C.
- 6. redox graphene/TiO as claimed in claim 12The preparation method of composite photocatalyst material, it is characterised in that In composite photocatalyst material, the mass ratio of redox graphene/titanium dioxide is 1：10~200.
- 7. redox graphene/TiO described in a kind of one of claim 1 to 62The application of composite photocatalyst material, its feature It is, obtained redox graphene/TiO2Composite is used for degradation of formaldehyde.
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| CN201710825844.3A CN107519856A (en) | 2017-09-14 | 2017-09-14 | A kind of redox graphene/TiO2The preparation and application of composite photocatalyst material |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108607534A (en) * | 2018-05-08 | 2018-10-02 | 张家港英华材料科技有限公司 | The preparation method and composite photo-catalyst of composite photo-catalyst |
| CN110773142A (en) * | 2019-11-14 | 2020-02-11 | 嘉兴烯成新材料有限公司 | Preparation and application of reduced hydroxylated graphene composite semiconductor catalyst |
| CN111013582A (en) * | 2019-12-16 | 2020-04-17 | 浙江瀚光环保科技有限公司 | Nano titanium dioxide-graphene composite photocatalyst capable of efficiently degrading formaldehyde and preparation method thereof |
| CN111097398A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Catalytic composite material, preparation method thereof and catalytic oxidation method of cycloolefin |
| CN112156764A (en) * | 2020-09-15 | 2021-01-01 | 凯盛石墨碳材料有限公司 | Nano TiO (titanium dioxide)2Modified graphene oxide/organic bentonite composite material and preparation method thereof |
| CN112371174A (en) * | 2020-10-23 | 2021-02-19 | 上海伊纯实业有限公司 | Photocatalytic nanocomposite material and preparation method and application thereof |
| CN113756135A (en) * | 2021-08-25 | 2021-12-07 | 重庆纤维研究设计院股份有限公司 | TiO 22Preparation method of photocatalyst filter paper |
| CN114768786A (en) * | 2022-05-18 | 2022-07-22 | 深圳市康弘智能健康科技股份有限公司 | Binary composite material for visible light catalytic aldehyde removal and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108607534A (en) * | 2018-05-08 | 2018-10-02 | 张家港英华材料科技有限公司 | The preparation method and composite photo-catalyst of composite photo-catalyst |
| CN108607534B (en) * | 2018-05-08 | 2020-10-16 | 张家港英华材料科技有限公司 | Preparation method of composite photocatalyst and composite photocatalyst |
| CN111097398A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Catalytic composite material, preparation method thereof and catalytic oxidation method of cycloolefin |
| CN111097398B (en) * | 2018-10-29 | 2023-01-13 | 中国石油化工股份有限公司 | Catalytic composite material, preparation method thereof and catalytic oxidation method of cycloolefin |
| CN110773142A (en) * | 2019-11-14 | 2020-02-11 | 嘉兴烯成新材料有限公司 | Preparation and application of reduced hydroxylated graphene composite semiconductor catalyst |
| CN111013582A (en) * | 2019-12-16 | 2020-04-17 | 浙江瀚光环保科技有限公司 | Nano titanium dioxide-graphene composite photocatalyst capable of efficiently degrading formaldehyde and preparation method thereof |
| CN112156764A (en) * | 2020-09-15 | 2021-01-01 | 凯盛石墨碳材料有限公司 | Nano TiO (titanium dioxide)2Modified graphene oxide/organic bentonite composite material and preparation method thereof |
| CN112371174A (en) * | 2020-10-23 | 2021-02-19 | 上海伊纯实业有限公司 | Photocatalytic nanocomposite material and preparation method and application thereof |
| CN112371174B (en) * | 2020-10-23 | 2022-12-06 | 上海伊纯实业有限公司 | Photocatalytic nanocomposite material and preparation method and application thereof |
| CN113756135A (en) * | 2021-08-25 | 2021-12-07 | 重庆纤维研究设计院股份有限公司 | TiO 22Preparation method of photocatalyst filter paper |
| CN114768786A (en) * | 2022-05-18 | 2022-07-22 | 深圳市康弘智能健康科技股份有限公司 | Binary composite material for visible light catalytic aldehyde removal and preparation method thereof |
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