CN103949235A - Graphene/carbon nanotube/titanium dioxide composite photocatalyst and preparation method and applications thereof - Google Patents
Graphene/carbon nanotube/titanium dioxide composite photocatalyst and preparation method and applications thereof Download PDFInfo
- Publication number
- CN103949235A CN103949235A CN201410169650.9A CN201410169650A CN103949235A CN 103949235 A CN103949235 A CN 103949235A CN 201410169650 A CN201410169650 A CN 201410169650A CN 103949235 A CN103949235 A CN 103949235A
- Authority
- CN
- China
- Prior art keywords
- graphene
- titanium dioxide
- carbon nanotube
- preparation
- composite photocatalyst
- 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.)
- Pending
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a graphene/carbon nanotube/titanium dioxide composite photocatalyst and a preparation method and applications thereof. The photocatalyst is composed of graphene, carbon nanotubes and titanium dioxide powder, wherein the compounding ratio of the graphene and the carbon nanotubes in percentage by mass is respectively 1-10%; the titanium dioxide powder refers to micro-spherical particles, is of an anatase structure and has particle size of 20-100 nm. The preparation method of the photocatalyst is a solution reduction method. Compared with the prior art, the graphene has a large specific surface area, and the carbon nanotubes have high electrical conductivity, so that due to the synergistic effect of the graphene and the carbon nanotubes, the charge transfer rate of P25 nanoparticles can be promoted. The photocatalytic efficiency is greatly increased.
Description
Technical field
The present invention relates to a kind of graphene/carbon nanotube/titanium dioxide composite photocatalyst and its preparation method and application, belong to photocatalysis technology field.
Background technology
Photocatalysis technology is the basic nanometer technology being born at 20 century 70s, and in China's Mainland, we can call photochemical catalyst with this popular word of photocatalyst.Typical natural light catalyst is exactly our common chlorophyll, promotes that airborne carbon dioxide and hydration become oxygen and carbohydrate in the photosynthesis of plant.Generally speaking nano photo-catalytic technology is a kind of nano bionic technology, for the depollution of environment, and self-cleaning material, advanced new forms of energy, treatment of cancer, a plurality of Disciplinary Frontiers such as high efficiency is antibacterial.
In the world can be numerous as the material of photocatalyst, comprise titanium dioxide (TiO
2), zinc oxide (ZnO), tin oxide (SnO
2), zirconium dioxide (ZrO
2), the many oxide sulfide semiconductors such as cadmium sulfide (CdS), wherein titanium dioxide (Titanium Dioxide) because of its oxidability strong, stable chemical nature is nontoxic, becomes in the world the most hot nano photo-catalytic material.In early days, also once more use cadmium sulfide (CdS) and zinc oxide (ZnO) as photocatalyst material, but due to the two unstable chemcial property, can dissolve at the light-catalysed light that occurs simultaneously, the harmful metal ion of stripping has certain bio-toxicity, therefore developed country has seldom been used as them civilian catalysis material at present, the industrial photocatalysis field of part is also being used.
The titanium dioxide optical catalyst of the photocatalysis degradation organic contaminant of prior art, specific area and electric conductivity all not enough, have therefore caused existing catalyst effect poor.
Summary of the invention
The problems referred to above and the defect that for prior art, exist, the object of this invention is to provide graphene/carbon nanotube/titanium dioxide composite photocatalyst and its preparation method and application, to solve problems of the prior art.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of graphene/carbon nanotube/titanium dioxide composite photocatalyst, by Graphene, CNT and titanium dioxide powder, formed, wherein, the compositely proportional of Graphene and CNT is by percentage to the quality between 1～10%, titanium dioxide powder is micro-spherical particle, Anatase structure, particle diameter is distributed as 20～100nm.
The electric conductivity of Graphene and light conductive performance are all very excellent, and CNT also has good electric conductivity, therefore, by Graphene and carbon nano tube-doped in titanium dioxide powder, can obviously improve the conduction of velocity of electronics and photon, improve the speed of light-catalyzed reaction; Meanwhile, due to the larger specific area of Graphene, also can significantly improve the efficiency of light-catalyzed reaction.
As a kind of preferred version, the particle diameter of described titanium dioxide powder is distributed as 32～80nm.
A preparation method for graphene/carbon nanotube/titanium dioxide composite photocatalyst as described in the present invention, it comprises the steps:
A) by carbon nanotube dispersed in the aqueous solution of graphene oxide, make graphene oxide-carbon nano tube suspension;
B) graphene oxide-carbon nano tube suspension step being obtained in a) adds Ti (SO
4)
2in the aqueous solution, after fully mixing, add again the softex kw aqueous solution, mix;
C) regulate behind pH value to 0.1～0.3, in 100～150 ℃ of hydrothermal treatment consists 60～80 hours, obtain hydro-thermal crude product;
D) by step c) in the hydro-thermal crude product that obtains carry out centrifugation, joining quality is in the sodium chloride-containing of 40～60 times of described crude products and the deionized water solution of ethanol, after ion-exchange, carry out centrifugation, water and absolute ethyl alcohol wash respectively, and 60～80 ℃ dry;
E) by steps d) in the product that obtains with the speed of 1～3 ℃/min, be warming up to 350～450 ℃, heat 2～3 hours, obtain graphene/carbon nanotube/TiO
2composite photo-catalyst.
As a kind of preferred version, described Ti (SO
4)
2the molar concentration of the aqueous solution is 15～25M.
As a kind of preferred version, step b) in the mixed solution that obtains, Ti (SO
4)
2, softex kw and H
2the mol ratio of O is 1: (0.10～0.14): (100～120).
As a kind of preferred version, steps d) in, in the deionized water solution of described sodium chloride-containing and ethanol, the mol ratio of absolute ethyl alcohol, deionized water and sodium chloride is 1: 1: (0.1～0.2).
Being applied to of a kind of nanotube/titanium dioxide composite photocatalyst of graphene/carbon is as described in the present invention greater than under the radiation of visible light of 420nm at wavelength, formaldehyde degradation by photocatalytic oxidation process.
Compared with prior art, Graphene has large specific area, and CNT has high electric conductivity, due to the cooperative effect of Graphene and CNT, can promote P25 nano particle electric charge transfer rate, and photocatalysis efficiency improves greatly.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.The experimental technique of unreceipted actual conditions in the following example, conventionally according to normal condition or the condition of advising according to manufacturer.Unless otherwise indicated, otherwise percentage and umber calculate by weight, and raw materials used, reagent, solvent are commercially available prod.
Embodiment 1:
By carbon nanotube dispersed, in the aqueous solution of graphene oxide, the quality of controlling CNT is 2% of Graphene quality, makes graphene oxide-carbon nano tube suspension; It is the Ti (SO of 15M that the graphene oxide-carbon nano tube suspension obtaining in upper step is added to molar concentration
4)
2in the aqueous solution, after fully mixing, add again softex kw (CTAB) aqueous solution, control Ti (SO
4)
2, CTAB and H
2the mol ratio of O is 1: 0.1: 100, mixes; With alkene nitric acid, regulate after the pH value to 0.15 of the mixed liquor obtaining in step, in 100 ℃ of hydrothermal treatment consists 60 hours, obtain hydro-thermal crude product; The hydro-thermal crude product obtaining in upper step is carried out to centrifugation, joining quality is in the sodium chloride-containing of 40 times of described crude products and the deionized water solution of ethanol, after ion-exchange, carry out centrifugation, water and absolute ethyl alcohol wash respectively, 60 ℃ dry, wherein, the deionized water solution of sodium chloride-containing and ethanol in when preparation, the mol ratio that needs to control absolute ethyl alcohol, deionized water and sodium chloride is 1: 1: 0.1; The product obtaining in upper step is warming up to 350 ℃ with the speed of 1 ℃/min, heats 3 hours, obtain graphene/carbon nanotube/TiO
2composite photo-catalyst.
Embodiment 2:
By carbon nanotube dispersed, in the aqueous solution of graphene oxide, the quality of controlling CNT is 5% of Graphene quality, makes graphene oxide-carbon nano tube suspension; It is the Ti (SO of 20M that the graphene oxide-carbon nano tube suspension obtaining in upper step is added to molar concentration
4)
2in the aqueous solution, after fully mixing, add again softex kw (CTAB) aqueous solution, control Ti (SO
4)
2, CTAB and H
2the mol ratio of O is 1: 0.12: 110, mixes; With alkene nitric acid, regulate after the pH value to 0.2 of the mixed liquor obtaining in step, in 120 ℃ of hydrothermal treatment consists 70 hours, obtain hydro-thermal crude product; The hydro-thermal crude product obtaining in upper step is carried out to centrifugation, joining quality is in the sodium chloride-containing of 50 times of described crude products and the deionized water solution of ethanol, after ion-exchange, carry out centrifugation, water and absolute ethyl alcohol wash respectively, 70 ℃ dry, wherein, the deionized water solution of sodium chloride-containing and ethanol in when preparation, the mol ratio that needs to control absolute ethyl alcohol, deionized water and sodium chloride is 1: 1: 0.15; The product obtaining in upper step is warming up to 400 ℃ with the speed of 3 ℃/min, heats 2.5 hours, obtain graphene/carbon nanotube/TiO
2composite photo-catalyst.
Embodiment 3:
By carbon nanotube dispersed, in the aqueous solution of graphene oxide, the quality of controlling CNT is 10% of Graphene quality, makes graphene oxide-carbon nano tube suspension; It is the Ti (SO of 25M that the graphene oxide-carbon nano tube suspension obtaining in upper step is added to molar concentration
4)
2in the aqueous solution, after fully mixing, add again softex kw (CTAB) aqueous solution, control Ti (SO
4)
2, CTAB and H
2the mol ratio of O is 1: 0.14: 120, mixes; With alkene nitric acid, regulate after the pH value to 0.3 of the mixed liquor obtaining in step, in 150 ℃ of hydrothermal treatment consists 80 hours, obtain hydro-thermal crude product; The hydro-thermal crude product obtaining in upper step is carried out to centrifugation, joining quality is in the sodium chloride-containing of 60 times of described crude products and the deionized water solution of ethanol, after ion-exchange, carry out centrifugation, water and absolute ethyl alcohol wash respectively, 80 ℃ dry, wherein, the deionized water solution of sodium chloride-containing and ethanol in when preparation, the mol ratio that needs to control absolute ethyl alcohol, deionized water and sodium chloride is 1: 1: 0.2; The product obtaining in upper step is warming up to 450 ℃ with the speed of 3 ℃/min, heats 3 hours, obtain graphene/carbon nanotube/TiO
2composite photo-catalyst.
Finally be necessary described herein: above embodiment is only for being described in more detail technical scheme of the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.
Claims (7)
1. a graphene/carbon nanotube/titanium dioxide composite photocatalyst, it is characterized in that, Graphene in described catalyst and the compositely proportional of CNT are by percentage to the quality between 1～10%, titanium dioxide powder is micro-spherical particle, Anatase structure, particle diameter is distributed as 20～100nm.
2. graphene/carbon nanotube/titanium dioxide composite photocatalyst as claimed in claim 1, is characterized in that, the particle diameter of described titanium dioxide powder is distributed as 32～80nm.
3. a preparation method for graphene/carbon nanotube/titanium dioxide composite photocatalyst as claimed in claim 1 or 2, is characterized in that, comprises the steps:
A) by carbon nanotube dispersed in the aqueous solution of graphene oxide, make graphene oxide-carbon nano tube suspension;
B) graphene oxide-carbon nano tube suspension step being obtained in a) adds Ti (SO
4)
2in the aqueous solution, after fully mixing, add again the softex kw aqueous solution, mix;
C) regulate behind pH value to 0.1～0.3, in 100～150 ℃ of hydrothermal treatment consists 60～80 hours, obtain hydro-thermal crude product;
D) by step c) in the hydro-thermal crude product that obtains carry out centrifugation, joining quality is in the sodium chloride-containing of 40～60 times of described crude products and the deionized water solution of ethanol, after ion-exchange, carry out centrifugation, water and absolute ethyl alcohol wash respectively, and 60～80 ℃ dry;
E) by steps d) in the product that obtains with the speed of 1～3 ℃/min, be warming up to 350～450 ℃, heat 2～3 hours, obtain graphene/carbon nanotube/TiO
2composite photo-catalyst.
4. preparation method as claimed in claim 3, is characterized in that, described Ti (SO
4)
2the molar concentration of the aqueous solution is 15～25M.
5. preparation method as claimed in claim 3, is characterized in that, step b) in the mixed solution that obtains, Ti (SO
4)
2, softex kw and H
2the mol ratio of O is 1: (0.10～0.14): (100～120).
6. preparation method as claimed in claim 3, is characterized in that, steps d) in, in the deionized water solution of described sodium chloride-containing and ethanol, the mol ratio of absolute ethyl alcohol, deionized water and sodium chloride is 1: 1: (0.1～0.2).
A graphene/carbon nanotube/titanium dioxide composite photocatalyst as claimed in claim 1 or 2 be applied at wavelength, be greater than under the radiation of visible light of 420nm, formaldehyde degradation by photocatalytic oxidation process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410169650.9A CN103949235A (en) | 2014-04-21 | 2014-04-21 | Graphene/carbon nanotube/titanium dioxide composite photocatalyst and preparation method and applications thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410169650.9A CN103949235A (en) | 2014-04-21 | 2014-04-21 | Graphene/carbon nanotube/titanium dioxide composite photocatalyst and preparation method and applications thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103949235A true CN103949235A (en) | 2014-07-30 |
Family
ID=51326661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410169650.9A Pending CN103949235A (en) | 2014-04-21 | 2014-04-21 | Graphene/carbon nanotube/titanium dioxide composite photocatalyst and preparation method and applications thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103949235A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104096553A (en) * | 2014-07-31 | 2014-10-15 | 武汉市意朗一品生物环保科技有限公司 | Titanium dioxide solution based on grapheme component and preparation method thereof |
| CN106582626A (en) * | 2015-10-15 | 2017-04-26 | 济南大学 | Preparation method and application of novel silver ion doped TiO2 composite material |
| CN106622236A (en) * | 2017-01-03 | 2017-05-10 | 昆明理工大学 | Preparation method of nanometer cuprous oxide particle-loaded type carbon nanotube-graphene material for photocatalysis |
| CN106744807A (en) * | 2016-11-25 | 2017-05-31 | 徐州得铸生物科技有限公司 | A kind of nanoscale composite carbon and its application in terms of heavy metal-polluted soil reparation |
| CN107174919A (en) * | 2017-06-28 | 2017-09-19 | 中国航发北京航空材料研究院 | The composite mesopore carbosphere air purifying preparation that graphene is modified |
| CN108579737A (en) * | 2018-01-30 | 2018-09-28 | 广东工业大学 | A kind of preparation method of the titanium dioxide of decorated by nano-gold-carbon nanotube composite photo-catalyst |
| CN108772045A (en) * | 2018-07-12 | 2018-11-09 | 山东佳星环保科技有限公司 | The preparation method for the composite porous microspheres air purifying preparation that graphene is modified |
| CN110092437A (en) * | 2019-04-09 | 2019-08-06 | 华东师范大学 | The biodegrading process of antibiotic in a kind of kitchen garbage, waste-water |
| CN111944337A (en) * | 2020-08-10 | 2020-11-17 | 天津单从新材料科技有限公司 | Heatable photocatalyst coating and preparation method thereof |
| CN112169784A (en) * | 2020-09-23 | 2021-01-05 | 宁波石墨烯创新中心有限公司 | Titanium dioxide/graphene/carbon composite material and preparation method and application thereof |
| CN114029045A (en) * | 2021-11-30 | 2022-02-11 | 河海大学 | Photocatalyst prepared by doping titanium dioxide with nano material and preparation method thereof |
-
2014
- 2014-04-21 CN CN201410169650.9A patent/CN103949235A/en active Pending
Non-Patent Citations (6)
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104096553A (en) * | 2014-07-31 | 2014-10-15 | 武汉市意朗一品生物环保科技有限公司 | Titanium dioxide solution based on grapheme component and preparation method thereof |
| CN106582626A (en) * | 2015-10-15 | 2017-04-26 | 济南大学 | Preparation method and application of novel silver ion doped TiO2 composite material |
| CN106744807A (en) * | 2016-11-25 | 2017-05-31 | 徐州得铸生物科技有限公司 | A kind of nanoscale composite carbon and its application in terms of heavy metal-polluted soil reparation |
| CN106744807B (en) * | 2016-11-25 | 2019-05-07 | 南京恒邦生物环保有限公司 | A kind of nanoscale composite carbon and its application in terms of heavy metal-polluted soil reparation |
| CN106622236A (en) * | 2017-01-03 | 2017-05-10 | 昆明理工大学 | Preparation method of nanometer cuprous oxide particle-loaded type carbon nanotube-graphene material for photocatalysis |
| CN106622236B (en) * | 2017-01-03 | 2019-04-09 | 昆明理工大学 | A kind of carbon nanotube-grapheme material preparation method of photocatalysis load nano cuprous oxide particle |
| CN107174919B (en) * | 2017-06-28 | 2020-06-02 | 中国航发北京航空材料研究院 | Graphene modified composite mesoporous carbon microsphere air purifying agent |
| CN107174919A (en) * | 2017-06-28 | 2017-09-19 | 中国航发北京航空材料研究院 | The composite mesopore carbosphere air purifying preparation that graphene is modified |
| CN108579737A (en) * | 2018-01-30 | 2018-09-28 | 广东工业大学 | A kind of preparation method of the titanium dioxide of decorated by nano-gold-carbon nanotube composite photo-catalyst |
| CN108772045A (en) * | 2018-07-12 | 2018-11-09 | 山东佳星环保科技有限公司 | The preparation method for the composite porous microspheres air purifying preparation that graphene is modified |
| CN110092437A (en) * | 2019-04-09 | 2019-08-06 | 华东师范大学 | The biodegrading process of antibiotic in a kind of kitchen garbage, waste-water |
| CN111944337A (en) * | 2020-08-10 | 2020-11-17 | 天津单从新材料科技有限公司 | Heatable photocatalyst coating and preparation method thereof |
| CN112169784A (en) * | 2020-09-23 | 2021-01-05 | 宁波石墨烯创新中心有限公司 | Titanium dioxide/graphene/carbon composite material and preparation method and application thereof |
| CN112169784B (en) * | 2020-09-23 | 2023-04-07 | 宁波石墨烯创新中心有限公司 | Titanium dioxide/graphene/carbon composite material and preparation method and application thereof |
| CN114029045A (en) * | 2021-11-30 | 2022-02-11 | 河海大学 | Photocatalyst prepared by doping titanium dioxide with nano material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103949235A (en) | Graphene/carbon nanotube/titanium dioxide composite photocatalyst and preparation method and applications thereof | |
| Wang et al. | Bioinspired synthesis of photocatalytic nanocomposite membranes based on synergy of Au-TiO2 and polydopamine for degradation of tetracycline under visible light | |
| Balachandran et al. | Facile construction of heterostructured BiVO4–ZnO and its dual application of greater solar photocatalytic activity and self-cleaning property | |
| Liu et al. | Tunable photocatalytic selectivity of hollow TiO2 microspheres composed of anatase polyhedra with exposed {001} facets | |
| Yin et al. | Synthesis and photocatalytic properties of fibrous titania prepared from protonic layered tetratitanate precursor in supercritical alcohols | |
| Gunti et al. | Nanostructured photocatalysis in the visible spectrum for the decontamination of air and water | |
| Wang et al. | Synthesis, characterization, and photocatalytic activities of titanate nanotubes surface-decorated by zinc oxide nanoparticles | |
| CN102863020B (en) | Preparation method of hollow titanium dioxide material | |
| Mohtar et al. | Impact of doping and additive applications on photocatalyst textural properties in removing organic pollutants: A review | |
| CN106076392A (en) | A kind of titanium dioxide/g C3n4the preparation method of quantum dot composite catalyst | |
| CN104941621A (en) | Composite photocatalyst for efficiently degrading antibiotics as well as preparation method and application thereof | |
| Jaleel et al. | Statistical and experimental studies of MoS 2/gC 3 N 4/TiO 2: A ternary Z-scheme hybrid composite | |
| Jongprateep et al. | Nanoparticulate titanium dioxide synthesized by sol–gel and solution combustion techniques | |
| CN108479752A (en) | A kind of BiVO of two dimension carbon-coating load4/TiO2The preparation method of heterogeneous visible light catalyst | |
| Singh et al. | Surface modification or doping of WO3 for enhancing the photocatalytic degradation of organic pollutant containing wastewaters: A review | |
| CN103691433A (en) | Ag-doped TiO2 material, and preparation method and application thereof | |
| CN102527366A (en) | Titanium dioxide nanotube graphene mixed photocatalyst and preparation method thereof | |
| Deng et al. | TiO2/reduced hydroxylated graphene nanocomposite photocatalysts: Improved electron–hole separation and migration | |
| CN105817241A (en) | Method for preparing copper phosphotungstate@titanium dioxide core-shell structured nanomaterial | |
| Sabbagh et al. | Synthesis of TiO2 (B) and High‐temperature Stable Anatase TiO2 Nanowires by Hydrothermal Method and Investigation of Photocatalytic Activity | |
| CN101947440A (en) | Preparation method of boron-doped modified TiO2 photocatalyst | |
| CN103934010B (en) | The preparation method of diverse microcosmic appearance bismuth phosphate photocatalyst | |
| CN107649108B (en) | Visible light photocatalyst and preparation method thereof | |
| Zhang et al. | Reduced Graphene Oxide–Titanium Dioxide Nanocomposites: Structural Characterization and Photocatalytic Degradation of Gaseous Formaldehyde | |
| CN101613125B (en) | Preparation method of anatase TiO2 nanowires |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140730 |
|
| WD01 | Invention patent application deemed withdrawn after publication |