CN101347724B - Carbon 60/titanium dioxide nano compound photocatalyst as well as preparation method and use thereof - Google Patents
Carbon 60/titanium dioxide nano compound photocatalyst as well as preparation method and use thereof Download PDFInfo
- Publication number
- CN101347724B CN101347724B CN2008100489046A CN200810048904A CN101347724B CN 101347724 B CN101347724 B CN 101347724B CN 2008100489046 A CN2008100489046 A CN 2008100489046A CN 200810048904 A CN200810048904 A CN 200810048904A CN 101347724 B CN101347724 B CN 101347724B
- Authority
- CN
- China
- Prior art keywords
- carbon
- solution
- nano compound
- deionized water
- titanium dioxide
- 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.)
- Expired - Fee Related
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a C60/ titanium dioxide nano-composite photocatalyst, a preparation method and the application thereof; the compound proportion by weight percentage of C60 in the composite photocatalyst is between 0.75-12 wt%; the titanium dioxide powder is microspheres granules and has anatase phase structure, and the grain diameter distributes between 20-75nm; the composite photocatalyst can be absorbed in the visible region with wave length of 400-800nm. The preparation method combines the hydrothermal method and the ion-exchange method to in-situ synthesize the C60/ titanium dioxide nano-composite photocatalyst and can load Pt on the surface of the C60/ titanium dioxide nano-composite photocatalyst by deposition. The bonding force of C60 and TiO2 nano particles in the produced composite photocatalyst is strong; the composite photocatalyst has high hydrogen production efficiency by visible-light photocatalysis and can be used for photocatalysis hydrogen production with theirradiation of visible light with wave length which is larger than 420nm and the existence of electronic scarifying agents.
Description
Technical field
The invention discloses a kind of visible light-responded carbon 60/ titanic oxide nano compound photocatalyst and its production and use that has, belong to the preparation and the applied technical field of nano-photocatalyst.
Background technology
The energy and environmental problem are the puzzlement whole mankind's significant problems.And Hydrogen Energy is that a kind of reserves are abundant, free of contamination novel energy.At present, the preparation method of hydrogen mainly contains water electrolysis hydrogen production, methane steam reforming hydrogen manufacturing, coke system water-gas, biological hydrogen production and photocatalysis hydrogen production etc.Wherein photocatalysis hydrogen production is a kind of emerging energy conversion technology.It mainly is to utilize semiconductor light-catalyst to produce electron-hole pair under the exciting of ultraviolet or visible light, and these electron-hole pairs have extremely strong reduction and oxidability, can be hydrogen and oxygen with water decomposition directly.Therefore, along with the development of photocatalysis technology, effectively utilize sunshine and directly from water or its relevant solution, obtain the important subject that clean energy resource-Hydrogen Energy is considered to a high risk and high reward.
Extensively and effectively using of photocatalysis hydrogen production depended on the catalytic efficiency of photochemical catalyst and to the utilization ratio of visible light.At present, titanium dioxide (TiO
2) stable because of its chemical property, fast light burn into is inexpensive, nontoxic etc., and advantage is subjected to showing great attention to of people always.Yet, TiO
2Forbidden band broad (3.2eV), can only absorb ultraviolet light (＜387nm).(300～400nm) only account for 4% of the solar energy that reaches ground to this luminous energy, and solar energy utilization ratio is very low.So, TiO
2Sensitization be a problem with theory significance and application prospect.At present, mainly contain organic dye sensitized, compound, metal ion/nonmetallic ion-doped etc. at the sensitization of wide band gap semiconducter with narrow gap semiconductor.
The research of C60 and fullerene compound is the current active research of ten minutes in the world field.Since nineteen ninety was realized the preparation of C60 convention amount, it had all caused chemists' very big interest at each ambit.The C60 distinctive molecular structure determines the sub-property of its short of electricity.In electron transfer reaction, C60 is generally as electron acceptor.Once there was the direct sunshine between C60 and the amine electron donor to induce the research of electron transfer reaction to report [J Am Chem Soc, 1992,114 (6): 2277-2279].In addition, C60 can absorb visible light, can be used as the spectral absorption scope that sensitizer is used to expand wide band gap semiconducter.
Find that through the document investigation about fullerene-titanium dioxide, especially carbon 60/ titanium dioxide (is C60/TiO
2) preparation method and the application thereof of nano composite photo-catalyst, have only [J.Phys.Chem.B1997,101,4422-4427 such as Kamat at present; J.Phys.Chem.1994,98,9137-9142] once reported a kind of preparation method of carbon 60/ titanic oxide nano compound material, this method is that carbon 60 is scattered in benzene or the toluene solution, add titanium dioxide powder to it then, stirring also will obtain composite behind the solvent evaporate to dryness.Use poisonous raw material but this method is a large amount of, and carbon 60 and the just simple mixing of titanium dioxide in the building-up process, both do not form chemical bonding, are unfavorable for the quick transmission of electronics in the photocatalytic process, thereby influence its photocatalysis effect.But also there is not other can make the problems referred to above improved so far, with C60/TiO
2Photocatalysis hydrogen production is used relevant report under nano composite photo-catalyst and preparation method thereof and the visible light condition.
Summary of the invention
The objective of the invention is at existing C 60/TiO
2The problem that exists among the preparation method of nano composite photo-catalyst provides a kind of C60 and TiO
2Between the nano particle in conjunction with C60/TiO strong, that higher visible light catalytic hydrogen production efficiency is arranged
2Nano composite photo-catalyst and its production and use.This method is easy and simple to handle, and cost is low, the C60/TiO that makes
2Nano composite photo-catalyst has higher heat endurance and excellent visible light photocatalysis and produces hydrogen activity, can be used for wavelength greater than the radiation of visible light of 420nm under and electronics sacrifice in the presence of the reagent photocatalysis hydrogen production.
The compositely proportional of C60 is by percentage to the quality between 0.75～12wt% in carbon 60/ titanic oxide nano compound photocatalyst provided by the invention, all the other are titanium dioxide, titanium dioxide powder is a micro-spherical particle, the anatase phase structure, particle diameter is distributed between 20～75nm, and composite photo-catalyst is that the visible region of 400-800nm all has absorption at wavelength.
The present invention also provides the method for preparing this carbon 60/ titanic oxide nano compound photocatalyst, and its concrete steps are as follows:
1) get C60 by the compositely proportional in the claim 1, and C60 is added weight percent concentration is that rare nitric acid of 5～15wt% boils to making it functionalized, centrifugation, 60～80 ℃ dry the C60 after handling; 2) with Ti (SO
4)
2Water-soluble mass percent concentration is 15～25% Ti (SO
4)
2Solution, the C60 after add handling, vigorous stirring is fully mixed both, and then adds softex kw, i.e. CTAB solution, in the mixed solution with molar ratio computing Ti (SO
4)
2: CTAB:H
2O=1:0.10～0.14:100～120;
3) pH that regulates mixed solution with rare nitric acid is 0.1～0.3, after continuing to mix, in 100～150 ℃ of hydrothermal treatment consists 60～80 hours, the hydro-thermal crude product;
4) with the centrifugation of hydro-thermal crude product, join mass ratio then and be in 40～60 times the deionized water and ethanolic solution of sodium chloride, fully after the ion-exchange, centrifugation, water and absolute ethyl alcohol wash respectively, 60～80 ℃ of dryings, wherein the mol ratio of the deionized water of used sodium chloride and ethanolic solution is an absolute ethyl alcohol: deionized water: sodium chloride=1:1:0.1～0.2;
5) with dried product exhibited in 350～450 ℃ of heat treatments 2～3 hours, heating rate is 1～3 ℃/min, obtains carbon 60/ titanic oxide nano compound photocatalyst.
And, press mass ratio H
2PtCl
6: photochemical catalyst is the ratio of 0.0105～0.105:1, and it is 3.45 * 10 that carbon 60/ titanic oxide nano compound photocatalyst that makes is added concentration
-5～3.45 * 10
-4The H of mol/l
2PtCl
6Deionized water and methanol solution, under ultraviolet light source, expose to H
2PtCl
6Decompose and heavy the collection at catalyst surface, make carbon 60/ titanic oxide nano compound photocatalyst area load that Pt be arranged, the percentage that the Pt of institute's load accounts for the catalyst gross mass after the supporting Pt is 0.5～5wt%, wherein used H
2PtCl
6Deionized water and methanol solution in the volume ratio of methyl alcohol and deionized water be methyl alcohol: deionized water=1:5～7.And used ultraviolet light source is that power is low pressure, high-pressure sodium lamp or ultraviolet germicidal lamp or the black light lamp of 125～500W.
As shown from the above technical solution, the present invention adopts hydro-thermal method and ion-exchange combination, and original position is synthesized C60/TiO
2Nano composite material, this method are the template agent first with the surfactant, adopt the hydro-thermal synthetic technology to add Ti (SO through the C60 that hydroxylating is handled
4)
2And the mixed system of surfactant (CTAB), the compound preparation C60/TiO of original position
2Nano composite photo-catalyst, this method are with chemical bonding mode fixed carbon 60, C60 and TiO at titanium dioxide surface
2In conjunction with stronger, show stable and good photocatalysis and produce hydrogen activity between the nano particle, have higher visible light catalytic hydrogen production efficiency.
Compare with existing photochemical catalyst and hydrogen producing technology, the present invention has the following advantages and effect:
1) not comprise poisonous solution, working condition gentleness, energy consumption and cost low for raw material, is fit to suitability for industrialized production.
2) utilize the template action of surfactant, by the composite visible-light absorptivity height that Hydrothermal Preparation obtains, specific area is bigger, is expected to be applied in the fields such as photocatalytic degradation pollutant, photodissociation water, photovoltaic solar cells.
3) the pure TiO of Pt load
2And C60 can not realize that all hydrogen is produced in photocatalysis under the visible light condition; By behind C60 compound, TiO
2Can absorb visible light and realize producing the hydrogen effect.Wherein, compositely proportional is the C60/TiO of 6.0wt%
2Photochemical catalyst has shown the highest photocatalytic activity.
4) the compound latter's the light abstraction width of not only can expanding of original position by carbon 60 and titanium dioxide is to visible light, and can quicken the transmission of light induced electron, effectively degradation of contaminant and photocatalysis hydrogen production under the visible light condition show good application prospects aspect visible light catalytic hydrogen manufacturing.
Description of drawings
Fig. 1 is gained C60/TiO of the present invention
2Nano composite photo-catalyst and nano-TiO
2The diffuse reflection abosrption spectrogram.
Fig. 2 is the C60/TiO of embodiment 1 preparation
2Electronic transmission Electronic Speculum (TEM) photo of nano composite photo-catalyst.
Fig. 3 is the C60/TiO of embodiment 2 preparations
2Electronic transmission Electronic Speculum (TEM) photo of nano composite photo-catalyst.
Fig. 4 is the C60/TiO of embodiment 3 preparations
2Electronic transmission Electronic Speculum (TEM) photo of nano composite photo-catalyst.
The specific embodiment
Embodiment 1: the C60 of 30mg is added boil a period of time in rare nitric acid that concentration is 5wt% and make it functionalized, centrifugation, 60 ℃ of oven dry.With Ti (SO
4)
2Mass percent concentration soluble in water is 15% Ti (SO
4)
2Solution adds the C60 after handling, and vigorous stirring 2 hours is fully mixed both, and then adds CTAB solution, and the mol ratio of each component is Ti (SO in the mixed solution
4)
2: CTAB:H
2O=1:0.10:100.With rare nitric acid regulator solution pH value is 0.3, after continuing to mix, 100 ℃ of hydrothermal treatment consists 60 hours, the hydro-thermal crude product.After the crude product centrifugation that hydro-thermal reaction is obtained, join in the deionized water/ethanolic solution of sodium chloride of 80g and carry out sufficient ion-exchange.The molar ratio of the deionized water/ethanolic solution of sodium chloride is an ethanol: deionized water: sodium chloride=1:1:0.1.Centrifugation is respectively washed respectively 3 times with distilled water and absolute ethyl alcohol.60 ℃ of dryings, 350 ℃ of heat treatment 2 hours, heating rate is 2 ℃/min, obtains the C60/TiO that compositely proportional is 1.5wt%
2Composite photo-catalyst.
Fig. 1 is gained C60/TiO
2Nano-composite catalyst diffuse reflection abosrption spectrogram, Fig. 2 is its TEM photo.With pure TiO
2Compare the C60/TiO of 1.5wt%
2Composite photo-catalyst has tangible absorption in 400～800nm scope, visible region absorption region broad is mainly derived from the contribution of C60, shows that it has visible absorption and catalytic activity.Titanium dioxide powder is a micro-spherical particle, and particle size distribution range is 25～75nm, and average grain diameter is 50nm, the anatase phase structure, have between particle loose structure in the reunion hole and particle, specific area is bigger, is of value to the particle transmission in the photocatalytic process and the raising of catalytic efficiency.The hydrogen generation efficiency of radiation of visible light after two hours is 190.6 μ mol/gh.And the pure TiO of Pt load
2Reach C60 and all can not realize photodissociation aquatic products hydrogen under the visible light condition, C60/TiO is described
2Nano composite photo-catalyst has good application prospects aspect the visible light catalytic hydrogen manufacturing.
Embodiment 2: the C60 of 60mg is added boil a period of time in rare nitric acid that concentration is 10wt% and make it functionalized, centrifugation, 70 ℃ of oven dry.With Ti (SO
4)
2Mass percent concentration soluble in water is 20% Ti (SO
4)
2Solution adds the C60 after handling, vigorous stirring 2 hours.And then adding CTAB solution, the mol ratio of each component is Ti (SO in the mixed solution
4)
2: CTAB:H
2O=1:0.12:110.With rare nitric acid regulator solution pH is 0.2, after continuing to mix, and 120 ℃ of hydrothermal treatment consists 72 hours.After the crude product centrifugation that hydro-thermal reaction is obtained, join in the deionized water/ethanolic solution of sodium chloride of 100g and carry out sufficient ion-exchange.The molar ratio of the deionized water/ethanolic solution of sodium chloride is an ethanol: deionized water: sodium chloride=1:1:0.15.To respectively wash respectively three times with distilled water and absolute ethyl alcohol after the product centrifugation after the ion-exchange.After 70 ℃ of dryings, 400 ℃ of heat treatment 3 hours, heating rate is 2 ℃/min, obtains the C60/TiO that compositely proportional is 3.0wt%
2Nano composite photo-catalyst.
Fig. 1 is gained 3.0wt%C60/TiO
2Nano-composite catalyst diffuse reflection abosrption spectrogram, Fig. 3 is its TEM photo.With pure TiO
2Compare the C60/TiO of 3.0wt%
2Composite photo-catalyst has tangible absorption in 400～800nm scope, visible region absorption region broad is mainly derived from the contribution of C60, shows to have visible absorption and catalytic activity.TiO
2The particle size distribution range of nano particle is 20～70nm, and average grain diameter is 40nm, has between particle loose structure in the reunion hole and particle, and specific area is bigger, is of value to the particle transmission in the photocatalytic process and the raising of catalytic efficiency.The hydrogen generation efficiency of radiation of visible light after two hours is 535.5 μ mol/gh.
Embodiment 3: the C60 of 120mg is added boil a period of time in rare nitric acid that concentration is 15wt% and make it functionalized, centrifugation, 80 ℃ of oven dry.With Ti (SO
4)
2Mass percent concentration soluble in water is 20% Ti (SO
4)
2Solution added C60 after a certain amount of processing and vigorous stirring 2 hours.In mixed system, add CTAB solution.The mol ratio of each component is Ti (SO in the mixed system
4)
2: CTAB:H
2O=1:0.14:120.With rare nitric acid regulator solution pH is 0.1, after continuing to mix, and 150 ℃ of hydrothermal treatment consists 80 hours.After the crude product centrifugation that hydro-thermal reaction is obtained, join in the deionized water/ethanolic solution of sodium chloride of 120g and carry out sufficient ion-exchange.The molar ratio of the deionized water/ethanolic solution of sodium chloride is an ethanol: deionized water: sodium chloride=1:1:0.2.To respectively wash respectively three times with distilled water and absolute ethyl alcohol after the product centrifugation after the ion-exchange.After 80 ℃ of dryings, 450 ℃ of heat treatment 3 hours, heating rate is 3 ℃/min, obtains the C60/TiO that compositely proportional is 6.0wt%
2Composite photo-catalyst.
Fig. 1 and Fig. 4 are respectively gained 6.0wt%C60/TiO
2Nano-composite catalyst diffuse reflection abosrption spectrogram and TEM photo.With pure TiO
2Compare the C60/TiO of 6.0wt% with the composite of other embodiment preparations
2The absorption of composite photo-catalyst in 400～800nm scope is significantly improved, and the visible region absorption efficiency is higher.TiO
2The particle size distribution range of nano particle is 20～75nm, and average grain diameter is 48nm, has between particle loose structure in the reunion hole and particle, and specific area is bigger, is of value to the particle transmission in the photocatalytic process and the raising of catalytic efficiency.The hydrogen generation efficiency of radiation of visible light after two hours is 553.3 μ mol/g.h.Compare with the composite of the foregoing description preparation, along with the raising photocatalytic activity of C60 compositely proportional obviously improves.
Embodiment 4: with the compositely proportional of embodiment 3 preparations is the C60/TiO of 6.0wt%
2Composite photo-catalyst is got 0.25g and is joined 3.45 * 10
-5The H of mol/l
2PtCl
6Deionized water and methanol solution (volume ratio is methyl alcohol: deionized water=1:7, H in the mixed solution
2PtCl
6With photochemical catalyst by quality ratio ratio be 0.0105), irradiation is 5 hours under 125W high pressure Hg lamp, filter, drying, promptly obtaining Pt load ratio is the C60/TiO of 0.5wt%
2Nano composite photo-catalyst.
Embodiment 5: with the compositely proportional of embodiment 3 preparations is the C60/TiO of 6.0wt%
2Composite photo-catalyst joins 6.90 * 10
-5The H of mol/l
2PtCl
6Deionized water and methanol solution (volume ratio is methyl alcohol: deionized water=1:6, H in the mixed solution
2PtCl
6With photochemical catalyst by quality ratio ratio be 0.021), in down irradiation 5 hours of 250W high pressure Hg lamp (also available low pressure mercury lamp or ultraviolet germicidal lamp or black light lamp), filter, drying, promptly obtaining Pt load ratio is the C60/TiO of 1.0wt%
2Nano composite photo-catalyst.
Embodiment 6: with the compositely proportional of embodiment 3 preparations is the C60/TiO of 6.0wt%
2Composite photo-catalyst joins 3.45 * 10
-4The H of mol/l
2PtCl
6Deionized water and methanol solution (volume ratio is methyl alcohol: deionized water=1:5, H in the mixed solution
2PtCl
6With photochemical catalyst by quality ratio ratio be 0.105), irradiation is 5 hours under 500W high pressure Hg lamp, filter, drying, promptly obtaining Pt load ratio is the C60/TiO of 5.0wt%
2Nano composite photo-catalyst.
Embodiment 7: the present invention has the C60/TiO of Pt to the area load of different C60 composite concentration
2Photochemical catalyst carries out visible light catalytic and produces the hydrogen experiment, to measure its photocatalytic activity.Be the contrast meter, also measured the pure TiO of Pt load
2And the hydrogen generation efficiency of C60 under the visible light condition.Hydrogen generation efficiency such as the table 1 of all kinds of samples under visible light, its concrete steps are: the pure TiO of 1wt%Pt load that takes by weighing 40mg respectively
2, pure C60 or C60 compositely proportional be 0.75%, 1.5%, 3.0%, 6.0% or 12.0% C60/TiO
2Composite photo-catalyst adds in the Photoreactor, and the triethanolamine (TEOA) that adds 85ml water and 15ml is sacrificed reagent as electronics, stirs and illumination 2 hours (light source is the 500W xenon lamp, has the optical filter of 420nm).The hydrogen content that adopts the gas chromatograph analysis to produce.Electronics is sacrificed reagent also can use CH
3OH, Na
2S or Na
2SO
3
The different composite concentration C 60/TiO of table 11.0wt%Pt load
2Photocatalysis hydrogen generation efficiency under the visible light condition
The result of table 1 shows, the pure TiO of Pt load
2And C60 all can not realize photodissociation aquatic products hydrogen under the visible light condition; And after C60 is compound, TiO
2Can absorb visible light photodissociation aquatic products hydrogen.In the prepared compositely proportional scope of the present invention, along with the raising of compositely proportional, hydrogen generation efficiency improves gradually, but the too high meeting of compositely proportional causes the reduction of hydrogen generation efficiency.Wherein, compositely proportional is the C60/TiO of 6.0wt%
2Photochemical catalyst has shown the highest visible light photocatalysis active.C60/TiO is described
2Nano composite photo-catalyst has good application prospects aspect the visible light catalytic hydrogen manufacturing.
Embodiment 8: the present invention has the 6.0wt%C60/TiO of different quality ratio Pt to area load
2Photochemical catalyst carries out visible light catalytic and produces the hydrogen experiment, to measure the influence of load different quality ratio Pt to its photocatalytic activity.For the contrast meter, also measured the not 6.0wt%C60/TiO of supporting Pt
2Hydrogen generation efficiency under the visible light condition.Hydrogen generation efficiency such as the table 2 of all kinds of samples under visible light, its concrete steps are: take by weighing the C60/TiO that embodiment 4,5,6 resulting Pt load ratios are respectively 0.5wt%, 1.0wt% and 5.0wt% respectively
2The nano composite photo-catalyst and the C60/TiO of supporting Pt not
2Nano composite photo-catalyst 40mg adds in the Photoreactor, and the triethanolamine (TEOA) that adds 85ml water and 15ml is sacrificed reagent as electronics, stirs and illumination 2 hours (light source is the 500W xenon lamp, has the optical filter of 420nm).The hydrogen content that adopts the gas chromatograph analysis to produce.Electronics is sacrificed reagent also can use CH
3OH, Na
2S or Na
2SO
3
The 6.0wt%C60/TiO of the different Pt load of table 2 ratio
2Photocatalysis hydrogen generation efficiency under the visible light condition
The result of table 2 shows, not the 6.0wt%C60/TiO of supporting Pt
2Photochemical catalyst can not be realized photodissociation aquatic products hydrogen under the visible light condition; And after the load of Pt, the 6.0wt%C60/TiO of supporting Pt
2Can realize visible light photodissociation aquatic products hydrogen.In the prepared Pt load proportion of the present invention, along with the raising of load ratio, hydrogen generation efficiency improves gradually, but the too high meeting of compositely proportional causes the reduction of hydrogen generation efficiency.Wherein, the supporting Pt ratio is the 6.0wt%C60/TiO of 1.0wt%
2Photochemical catalyst has shown the highest visible light photocatalysis active.
Claims (5)
1. carbon 60/ titanic oxide nano compound photocatalyst, it is characterized in that: the compositely proportional of carbon 60 is by percentage to the quality between 0.75～12wt% in the composite photo-catalyst, all the other are titanium dioxide, titanium dioxide powder is a micro-spherical particle, the anatase phase structure, particle diameter is distributed between 20～75nm, and composite photo-catalyst is that the visible region of 400-800nm all has absorption at wavelength, and carbon 60/ titanic oxide nano compound photocatalyst is by adopting the following steps preparation:
1) get carbon 60 by above-mentioned compositely proportional, and carbon 60 is added weight percent concentration is that rare nitric acid of 5～15wt% boils to making it functionalized, centrifugation, 60～80 ℃ dry the carbon 60 after handling;
2) with Ti (SO
4)
2Water-soluble mass percent concentration is 15～25% Ti (SO
4)
2Solution, the carbon 60 after add handling, vigorous stirring is fully mixed both, and then adds softex kw, i.e. CTAB solution, in the mixed solution with molar ratio computing Ti (SO
4)
2: CTAB: H
2O=1: 0.10～0.14: 100～120;
3) pH that regulates mixed solution with rare nitric acid is 0.1～0.3, after continuing to mix, in 100～150 ℃ of hydrothermal treatment consists 60～80 hours, the hydro-thermal crude product;
4) with the centrifugation of hydro-thermal crude product, join mass ratio then and be in 40～60 times the deionized water and ethanolic solution of sodium chloride, fully after the ion-exchange, centrifugation, water and absolute ethyl alcohol wash respectively, 60～80 ℃ of dryings, wherein the mol ratio of the deionized water of used sodium chloride and ethanolic solution is an absolute ethyl alcohol: deionized water: sodium chloride=1: 1: 0.1～0.2;
5) with dried product exhibited in 350～450 ℃ of heat treatments 2～3 hours, heating rate is 1～3 ℃/min, obtains carbon 60/ titanic oxide nano compound photocatalyst.
2. carbon 60/ titanic oxide nano compound photocatalyst, it is characterized in that: at the described composite photo-catalyst area load of claim 1 mass percent being arranged is the Pt of 0.5～5wt%.
3. the preparation method of described carbon 60/ titanic oxide nano compound photocatalyst of claim 1 is characterized in that adopting step as follows:
1) get carbon 60 by the compositely proportional in the claim 1, and carbon 60 is added weight percent concentration is that rare nitric acid of 5～15wt% boils to making it functionalized, centrifugation, 60～80 ℃ dry the carbon 60 after handling;
2) with Ti (SO
4)
2Water-soluble mass percent concentration is 15～25% Ti (SO
4)
2Solution, the carbon 60 after add handling, vigorous stirring is fully mixed both, and then adds softex kw, i.e. CTAB solution, in the mixed solution with molar ratio computing Ti (SO
4)
2: CTAB: H
2O=1: 0.10～0.14: 100～120;
3) pH that regulates mixed solution with rare nitric acid is 0.1～0.3, after continuing to mix, in 100～150 ℃ of hydrothermal treatment consists 60～80 hours, the hydro-thermal crude product;
4) with the centrifugation of hydro-thermal crude product, join mass ratio then and be in 40～60 times the deionized water and ethanolic solution of sodium chloride, fully after the ion-exchange, centrifugation, water and absolute ethyl alcohol wash respectively, 60～80 ℃ of dryings, wherein the mol ratio of the deionized water of used sodium chloride and ethanolic solution is an absolute ethyl alcohol: deionized water: sodium chloride=1: 1: 0.1～0.2;
5) with dried product exhibited in 350～450 ℃ of heat treatments 2～3 hours, heating rate is 1～3 ℃/min, obtains carbon 60/ titanic oxide nano compound photocatalyst.
4. the purposes of described carbon 60/ titanic oxide nano compound photocatalyst of claim 1 is characterized in that: be used for wavelength greater than the radiation of visible light of 420nm under and electronics sacrifice in the presence of the reagent photocatalysis hydrogen production.
5. according to the purposes of described carbon 60/ titanic oxide nano compound photocatalyst of claim 4, it is characterized in that: it is triethanolamine, CH that electronics is sacrificed reagent
3OH, Na
2S or Na
2SO
3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100489046A CN101347724B (en) | 2008-08-19 | 2008-08-19 | Carbon 60/titanium dioxide nano compound photocatalyst as well as preparation method and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100489046A CN101347724B (en) | 2008-08-19 | 2008-08-19 | Carbon 60/titanium dioxide nano compound photocatalyst as well as preparation method and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101347724A CN101347724A (en) | 2009-01-21 |
| CN101347724B true CN101347724B (en) | 2011-03-30 |
Family
ID=40266787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100489046A Expired - Fee Related CN101347724B (en) | 2008-08-19 | 2008-08-19 | Carbon 60/titanium dioxide nano compound photocatalyst as well as preparation method and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101347724B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120184B (en) * | 2011-01-25 | 2013-09-25 | 鄂尔多斯市联科清洁能源技术有限公司 | Noble metal-carrying titanium dioxide catalyst and preparation method and use thereof |
| CN102553560B (en) * | 2012-01-12 | 2013-12-04 | 哈尔滨工业大学 | Preparation method of titanium dioxide/graphene composite photocatalyst |
| CN102618219B (en) * | 2012-03-07 | 2014-03-05 | 日高（大连）节能照明有限公司 | Nanometer dustproof pretreating agent |
| CN102941106A (en) * | 2012-11-22 | 2013-02-27 | 上海师范大学 | Preparation method of C60/Bi2Tio4F2 composite photocatalyst |
| CN103359686B (en) | 2013-07-15 | 2015-04-22 | 中盈长江国际新能源投资有限公司 | Light-catalyzed reaction system for collecting sunlight |
| CN104128171B (en) * | 2014-07-02 | 2016-09-21 | 昆明理工大学 | A kind of composite of titanium dioxide and Linesless charcoal and preparation method thereof |
| CN104525173B (en) * | 2014-12-25 | 2016-08-24 | 东华大学 | A kind of CNT composite Ti O2the preparation method of green deep water treatment agent |
| CN105536763A (en) * | 2016-02-25 | 2016-05-04 | 深圳市飘爱健康科技有限公司 | Carbon-atom-doped titanium dioxide photocatalyst and preparation method thereof |
| JP6757060B2 (en) * | 2016-04-18 | 2020-09-16 | 国立研究開発法人産業技術総合研究所 | Visible light active titania-carbon particle composite and its manufacturing method |
| CN108479765A (en) * | 2018-01-23 | 2018-09-04 | 齐齐哈尔大学 | Counter opal structure Pt/TiO2-ZrO2Synthetic method |
| CN114602447A (en) * | 2022-03-28 | 2022-06-10 | 杭州师范大学 | Preparation method of fullerol/gold nanoparticle composite photocatalyst |
-
2008
- 2008-08-19 CN CN2008100489046A patent/CN101347724B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101347724A (en) | 2009-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101347724B (en) | Carbon 60/titanium dioxide nano compound photocatalyst as well as preparation method and use thereof | |
| CN101347725B (en) | Carbon nano-tube/titanic oxide nano compound photocatalyst and preparation method and application thereof | |
| Li et al. | Enhanced cocatalyst-support interaction and promoted electron transfer of 3D porous g-C3N4/GO-M (Au, Pd, Pt) composite catalysts for hydrogen evolution | |
| Wei et al. | Photocatalytic hydrogen evolution with simultaneous antibiotic wastewater degradation via the visible-light-responsive bismuth spheres-g-C3N4 nanohybrid: Waste to energy insight | |
| Yang et al. | Highly efficient photocatalytic hydrogen evolution and simultaneous formaldehyde degradation over Z-scheme ZnIn2S4-NiO/BiVO4 hierarchical heterojunction under visible light irradiation | |
| Wang et al. | Indirect Z-scheme BiOI/g-C3N4 photocatalysts with enhanced photoreduction CO2 activity under visible light irradiation | |
| Yang et al. | Visible light-driven photocatalytic H2 generation and mechanism insights into Bi2O2CO3/G-C3N4 Z-scheme photocatalyst | |
| Liu et al. | Easily and synchronously ameliorating charge separation and band energy level in porous g-C3N4 for boosting photooxidation and photoreduction ability | |
| Guo et al. | A highly active nano-micro hybrid derived from Cu-bridged TiO2/porphyrin for enhanced photocatalytic hydrogen production | |
| Chen et al. | In situ template-free ion-exchange process to prepare visible-light-active g-C3N4/NiS hybrid photocatalysts with enhanced hydrogen evolution activity | |
| Min et al. | Enhanced electron transfer from the excited eosin Y to mpg-C3N4 for highly efficient hydrogen evolution under 550 nm irradiation | |
| Wu et al. | Novel Bi2Sn2O7 quantum dots/TiO2 nanotube arrays S-scheme heterojunction for enhanced photoelectrocatalytic degradation of sulfamethazine | |
| Cui et al. | Enhanced surface electron transfer by fabricating a core/shell Ni@ NiO cluster on TiO2 and its role on high efficient hydrogen generation under visible light irradiation | |
| He et al. | NH2-MIL-125 (Ti) encapsulated with in situ-formed carbon nanodots with up-conversion effect for improving photocatalytic NO removal and H2 evolution | |
| Zhao et al. | Construction and enhanced efficiency of Z-scheme-based ZnCdS/Bi2WO6 composites for visible-light-driven photocatalytic dye degradation | |
| Yu et al. | Rational design and fabrication of TiO2 nano heterostructure with multi-junctions for efficient photocatalysis | |
| CN103007913A (en) | Preparation method of Ti<3+>-doped TiO2 composite graphene photocatalyst | |
| Wang et al. | CoAl LDH in-situ derived CoAlP coupling with Ni2P form S-scheme heterojunction for efficient hydrogen evolution | |
| Deng et al. | The pivotal role of defects in fabrication of polymeric carbon nitride homojunctions with enhanced photocatalytic hydrogen evolution | |
| Ma et al. | An efficient photocatalytic system under visible light: In-situ growth cocatalyst Ni2P on the surface of CdS | |
| Su et al. | Efficient photocatalytic production of hydrogen peroxide by Z-scheme resorcinol-formaldehyde resin/g-C3N4 heterostructure under visible light | |
| Jiang et al. | ZIF-9 derived cobalt phosphide and In2O3 as co-catalysts for efficient hydrogen production | |
| Xiang et al. | Rational construction of Z‐scheme charge transfer based on 2D graphdiyne (g‐CnH2n− 2) coupling with amorphous Co3O4 quantum dots for efficient photocatalytic hydrogen generation | |
| Yu et al. | Construction of rutile/anatase TiO2 homojunction and metal-support interaction in Au/TiO2 for visible photocatalytic water splitting and degradation of methylene blue | |
| Huang et al. | Fabrication of CuS-modified inverse opal g-C3N4 photocatalyst with enhanced performance of photocatalytic reduction of CO2 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110330 Termination date: 20130819 |