CN102974333A - Preparation method of boron-doped graphene nano-sheet composite TiO2 photocatalyst - Google Patents
Preparation method of boron-doped graphene nano-sheet composite TiO2 photocatalyst Download PDFInfo
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- CN102974333A CN102974333A CN2012105363587A CN201210536358A CN102974333A CN 102974333 A CN102974333 A CN 102974333A CN 2012105363587 A CN2012105363587 A CN 2012105363587A CN 201210536358 A CN201210536358 A CN 201210536358A CN 102974333 A CN102974333 A CN 102974333A
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Abstract
The invention relates to a preparation method of a boron-doped graphene nano-sheet composite TiO2 photocatalyst. The preparation method comprises the following steps of: firstly, preparing a boron-doped graphene nano-sheet by adopting a method that vacuum reduction is combined with the ultrasonic; and secondly, directly compositing the P25 with the boron-doped graphene nano-sheet by adopting an ultrasonic mixing method. Compared with the prior art, the boron-doped graphene nano-sheet prepared by using the method has smaller nano-size and better dispersity, and due to the largely exposed edge, the loading of P25 nano particles at the edge of the graphene nano-sheet is facilitated. The boron-doped graphene nano-sheet has strong photoproduction electronic capability and electronic transmission capability; and the prepared novel boron-doped graphene nano-sheet composite P25 photocatalyst has strong photoproduction CO2 capability.
Description
Technical field
The present invention relates to the nano-photocatalyst material field, is take P25 cheap and easy to get, graphene oxide and boric acid as raw material, prepares a kind of novel high photo-reduction CO that has
2Performance, boron doped graphene nanometer sheet composite Ti O
2The new method of photochemical catalyst.
Background technology
Although TiO
2Have lot of advantages, but TiO
2Also there is the limitation that much can not be ignored in application in the multiphase photocatalysis field.TiO
2Maximum application limitation be it band-gap energy and the spectrum of sunshine extremely do not mate TiO
2Can only absorbing wavelength less than the ultraviolet light of 387nm.In order to overcome TiO
2This shortcoming, about to TiO
2Carry out the modification such as nonmetal, metal-doped is subject to people gradually to improve it to visible light-responded research concern.Yet the doping of traditional metal or nonmetallic ion can cause TiO
2The heat endurance variation, thereby and the trap of catching that can introduce electric charge produce mutually a large amount of electron-hole recombinations centers on the surface of catalyst with body.The more important thing is that traditional doping method energy consumption is high, and need to be equipped with expensive instrument, thereby this has greatly increased production cost and has been unfavorable for later suitability for industrialized production.
On the other hand, absolute two-dimensional material Graphene is owing to have excellent machinery, calorifics, optics and electric property, and greatly excited people to designing take Graphene as the basis, can be applicable to nanoelectronics, the interest of the new material of the technical fields such as hydrogen gas production and storage and photocatalysis.Graphene is owing to have the electrical properties more more excellent than CNT, and good electric conductivity and chemical stability, and is considered to the multifunctional material than the better transmission electronics of CNT or hole.Graphene is carried out the foreign atom doping vario-properties such as further boron, can change the characteristic electron of Graphene, make it have special PhotoelectrochemicalProperties Properties.Therefore, the doping vario-property Graphene is applied to TiO
2The modification of carrying out chemical property Deng semiconductor is the study hotspot of photocatalysis field.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of high sunshine reduction CO that has for the defective that overcomes above-mentioned prior art existence
2The boron doped graphene nanometer sheet composite Ti O of performance
2The preparation method of photochemical catalyst.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of boron doped graphene nanometer sheet composite Ti O
2The preparation method of photochemical catalyst, the method adopt cryogenic vacuum reduction and the ultrasonic preparation boron doped graphene nanometer sheet composite Ti O that combines take graphene oxide, gas phase titanium dioxide (P25) as presoma
2Photochemical catalyst specifically may further comprise the steps:
The preparation of boron doped graphene nanometer sheet
Measure the graphite oxide aqueous solution, be scattered in the ultra-pure water, behind the ultrasonic dispersion 1h, add again boric acid, 60 ℃ of lower evaporates to dryness behind the magnetic agitation 1h, sample behind the evaporate to dryness at 300 ℃ of lower vacuum reduction 3h, is scattered in the ultra-pure water, more ultrasonic 10h more again, in solution, add hydrochloric acid solution, after stirring 15h, with ultra-pure water sample is washed 4 times again, obtain boron doped graphene nanometer sheet;
Boron doped graphene nanometer sheet composite Ti O
2The preparation of photochemical catalyst
Boron doped graphene nanometer sheet is scattered in the ultra-pure water, and ultrasonic 1h adds gas phase titanium dioxide again, and mixed solution successively passes through ultrasonic 1h, and mechanical agitation 5h with 80 ℃ of lower oven dry of solution, grinds and obtains boron doped graphene nanometer sheet composite Ti O at last
2Photochemical catalyst.
The concentration of described graphite oxide aqueous solution is 2-3mg/ml.
The weight ratio of graphene oxide and boric acid is 0.01-0.015: 0.4.
Described graphite oxide aqueous solution adopts the Hummer method to prepare.
The concentration of described hydrochloric acid solution is 1M.
Described boron doped graphene nanometer sheet composite Ti O
2Photocatalyst sheet has higher light induced electron ability and electron transport ability, therefore has high sunshine reduction CO
2Performance can be under solar light irradiation, with CO
2Be reduced into methane.Its photo-reduction CO
2Activity will be apparently higher than Graphene and graphene oxide composite Ti O
2Photochemical catalyst.
Compared with prior art, the present invention has the following advantages:
1) with respect to traditional doping, the method for modifying such as compound, the ultrasonic mixing method equipment of vacuum reduction method agent is simple, greatly reduces production cost, is conducive to industrialization promotion.
2) the vacuum activating method can realize the modified with reduction to graphene oxide simultaneously, reaches the boron doping vario-property to Graphene.
3) owing to mixing, boron in the vacuum reduction process causes that Graphene produces defective, through ultrasonic post processing, can successfully resolve into graphene nanometer sheet with micron-sized Graphene.
4) boron doped graphene nanometer sheet can expose more edge and carboxylic group, has promoted TiO
2Nano particle is compound the Graphene surface.
5) boron doped graphene nanometer sheet has higher light induced electron ability and electron transport ability.
6) the boron doped graphene nanometer sheet composite Ti O of preparation
2Photochemical catalyst can be under solar light irradiation, with CO
2Be reduced into methane.Its photo-reduction CO
2Activity will be apparently higher than Graphene and graphene oxide composite Ti O
2Photochemical catalyst.
Description of drawings
Fig. 1 is the TEM photo of the boron doped graphene of embodiment 1 preparation.
Fig. 2 is the graphene oxide of embodiment 1 preparation and the XRD spectra of boron doped graphene and GO.
Fig. 3 is the B1s XPS spectrum figure of the boron doped graphene of embodiment 1 preparation.
Fig. 4 is the TEM photo of the compound P25 photochemical catalyst of boron doped graphene nanometer sheet of embodiment 1 preparation.
Fig. 5 is different Graphene composite Ti O
2The photoelectric current resolution chart of photochemical catalyst.
Fig. 6 is different Graphene composite Ti O
2Photochemical catalyst is photo-reduction CO under the simulated solar irradiation
2Activity figure.
The specific embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
The present invention adopts the cryogenic vacuum reducing process to prepare Novel series boron doped graphene nanometer sheet composite Ti O
2Photochemical catalyst.The vacuum reduction process can realize the modified with reduction to graphene oxide simultaneously, and the doping vario-property of boron atom pair Graphene.What is more important, vacuum-thermal reduction process can be destroyed the C=C key in the Graphene skeleton, and produce a large amount of defectives in the Graphene skeleton.After boron doped graphene nanometer sheet (B-GR) carried out further ultrasonic processing, the C=C key in the Graphene skeleton and the C=C key fracture in the defective just obtained B doped graphene nanometer sheet, and the size of nanometer sheet is greatly about about 30nm.Adopt ultrasonic mixing method that B doped graphene nanometer sheet and the P25 that makes is compound, finally obtain boron doped graphene nanometer sheet composite Ti O
2Photochemical catalyst.
The present invention is the above-mentioned photochemical catalyst of preparation, and the processing step that adopts is as follows:
1): preparation graphene oxide (GO)
" Hummer " method of employing prepares GO.
2): the preparation of boron doped graphene nanometer sheet
A certain amount of GO is scattered in the 40ml ultra-pure water, and ultrasonic dispersion 1h adds H again
3BO
3As the boron source.Evaporate to dryness behind the stirring 1h.The graphene oxide of drying is processed 3h 300 ℃ of lower vacuum reductions, again be scattered in again in the ultra-pure water ultrasonic dispersion 10h.Successively use HCl solution, the ultra-pure water washing sample is scattered in the 5ml ultra-pure water for several times at last, just obtains boron doped graphene nanometer sheet.
3): boron doped graphene nanometer sheet and TiO
2The preparation of composite photo-catalyst
Adopt ultrasonic mixing method that P25 and boron doped graphene are combined with each other.
Photo catalytic reduction CO provided by the invention
2The activity rating method is as follows:
CO
2The photo-reduction experiment is carried out in a homemade reaction unit.Detailed process is as follows: take by weighing the 0.1g catalyst and be scattered in the saturated CO of 5ml
2In the aqueous solution, add again the NaSO of 0.1g
3As hole trapping agents.The xenon lamp of 300W is as the simulated solar light source.Photo-reduction CO
2The methane that produces is to analyze with gas chromatograph (TechompGC-7890II, flame ionization ditector (FID)).
1): the preparation of graphene oxide (GO)
Adopt " Hummer " method to prepare GO, concrete grammar is as follows: 3g graphite is scattered in the concentrated sulfuric acid that 12ml contains 2.5g potassium peroxydisulfate and 2.5g phosphorus pentoxide, and 80 ℃ are stirred 4.5h, then are cooled to room temperature and normal temperature and place 12h.Gained mixture filtration washing and natural drying 12h.Pretreated graphite adds in the 120ml concentrated sulfuric acid, maintains the temperature to add while stirring 15g potassium permanganate below 20 ℃ 35 ℃ of lower 2h that stir.Mixture keeps temperature to be lower than 50 ℃ with 250ml deionized water dilution, ice-water bath.After stirring 2h, add the deionized water of 0.7L, slowly add subsequently the hydrogen peroxide of 20ml 30%.Mixed solution presents glassy yellow, and bubbling.Leave standstill, remove supernatant liquor, add 10% salt acid elution for several times, with the deionized water washing for several times until leave standstill be not easy sedimentation till, dialysed 10-15 days.The gained sample ultrasonic disperses to obtain homodisperse graphite oxide aqueous solution.
2): the preparation of Graphene (GR) and boron doped graphene nanometer sheet (B-GR)
Graduated cylinder is measured 5ml graphene oxide (GO, 2.1mg/ml), is scattered in the 20ml ultra-pure water, behind the ultrasonic dispersion 1h, adds 0.4g boric acid again, 60 ℃ of lower evaporates to dryness behind the magnetic agitation 1h.Sample behind the evaporate to dryness at 300 ℃ of lower vacuum reduction 3h, is scattered in the 20ml ultra-pure water, more ultrasonic 10h more again.Ultrasonic complete after, add the hydrochloric acid solution of 30ml 1M in the solution, stir 15h after, again with ultra-pure water with sample washing 4 times, at last with sample dispersion in the 5ml ultra-pure water, so just obtain boron doped graphene nanometer sheet, be labeled as B-GR.
3): boron doped graphene nanometer sheet composite Ti O
2The preparation of photochemical catalyst
Get 4ml B-GR nanometer sheet and be scattered in the 40ml ultra-pure water, ultrasonic 1h adds 0.5g P25 again.Mixed solution successively passes through ultrasonic 1h, mechanical agitation 5h.With 80 ℃ of lower oven dry of solution, grind and just obtain composite photo-catalyst at last, be labeled as: P25/B-GR.
Comparative Examples 1
The preparation method who adopts is identical with embodiment 1, but reduced graphene is under the prerequisite that does not add boric acid, adopts above identical test method to obtain, and the graphene nanometer sheet that obtains is labeled as GR.Then the step (3) of GR and P25 such as embodiment 1 is reacted, the product labelling that obtains is P25/GR.
Comparative Examples 2
Directly the step (3) of P25 such as embodiment 1 is reacted with GO, the product labelling that obtains is P25/GO.
Fig. 1 is the TEM photo of the boron doped graphene B-GR of embodiment 1 preparation.Fig. 1 shows that the boron doped graphene shows as the nano-sheet structure.Fig. 2 is graphene oxide and the boron doped graphene and XRD spectra GO of embodiment 1 preparation.Fig. 2 shows that the vacuum reduction method can well be reduced into Graphene with graphene oxide.Fig. 3 is the B1s XPS spectrum figure of the boron doped graphene of embodiment 1 preparation.Fig. 3 shows that boron mainly carries out doping vario-property in four kinds of modes to Graphene, shows as respectively the generation of four kinds of chemical bonds: B
4C, BC
3, C
2-B-OH, O=C-OB.Fig. 4 is the TEM photo of the compound P25 photochemical catalyst of boron doped graphene nanometer sheet of embodiment 1 preparation, and different resolution ratio is shown in A, B.Fig. 4 shows, composite Ti O
2The dispersiveness of boron doped graphene nanometer sheet become better and TiO
2Mainly be compounded in the edge of Graphene.Fig. 5 is different Graphene composite Ti O
2The photoelectric current resolution chart of photochemical catalyst.Fig. 5 shows that the compound P25 photochemical catalyst of boron doped graphene nanometer sheet has higher light induced electron ability and electron transport ability.Fig. 6 is the different Graphene composite Ti O of embodiment 1 preparation
2Photochemical catalyst is photo-reduction CO under the simulated solar irradiation
2Activity figure.Fig. 6 shows that the compound P25 photochemical catalyst of boron doped graphene nanometer sheet has higher photo-reduction CO
2Produce the ability of methane.
A kind of boron doped graphene nanometer sheet composite Ti O
2The preparation method of photochemical catalyst, the method adopt cryogenic vacuum reduction and the ultrasonic preparation boron doped graphene nanometer sheet composite Ti O that combines take graphene oxide, gas phase titanium dioxide (P25) as presoma
2Photochemical catalyst specifically may further comprise the steps:
The preparation of boron doped graphene nanometer sheet
Adopt the Hummer method to prepare the graphite oxide aqueous solution, the graphite oxide aqueous solution that to measure the above-mentioned concentration for preparing be 2mg/ml, be scattered in the ultra-pure water, behind the ultrasonic dispersion 1h, add again boric acid, the weight ratio of graphene oxide and boric acid is 0.01: 0.4,60 ℃ of lower evaporates to dryness behind the magnetic agitation 1h, sample behind the evaporate to dryness at 300 ℃ of lower vacuum reduction 3h, is scattered in the ultra-pure water, more ultrasonic 10h more again, the hydrochloric acid solution that adds 1M in the solution, after stirring 15h, with ultra-pure water sample is washed 4 times again, obtain boron doped graphene nanometer sheet;
Boron doped graphene nanometer sheet composite Ti O
2The preparation of photochemical catalyst
Boron doped graphene nanometer sheet is scattered in the ultra-pure water, and ultrasonic 1h adds gas phase titanium dioxide again, and mixed solution successively passes through ultrasonic 1h, and mechanical agitation 5h with 80 ℃ of lower oven dry of solution, grinds and obtains boron doped graphene nanometer sheet composite Ti O at last
2Photochemical catalyst, this boron doped graphene nanometer sheet composite Ti O
2Photocatalyst sheet has higher light induced electron ability and electron transport ability, therefore has high sunshine reduction CO
2Performance can be under solar light irradiation, with CO
2Be reduced into methane.Its photo-reduction CO
2Activity will be apparently higher than Graphene and graphene oxide composite Ti O
2Photochemical catalyst.
A kind of boron doped graphene nanometer sheet composite Ti O
2The preparation method of photochemical catalyst, the method adopt cryogenic vacuum reduction and the ultrasonic preparation boron doped graphene nanometer sheet composite Ti O that combines take graphene oxide, gas phase titanium dioxide (P25) as presoma
2Photochemical catalyst specifically may further comprise the steps:
The preparation of boron doped graphene nanometer sheet
Adopt the Hummer method to prepare the graphite oxide aqueous solution, the graphite oxide aqueous solution that to measure the above-mentioned concentration for preparing be 3mg/ml, be scattered in the ultra-pure water, behind the ultrasonic dispersion 1h, add again boric acid, the weight ratio of graphene oxide and boric acid is 0.015: 0.4,60 ℃ of lower evaporates to dryness behind the magnetic agitation 1h, sample behind the evaporate to dryness at 300 ℃ of lower vacuum reduction 3h, is scattered in the ultra-pure water, more ultrasonic 10h more again, the hydrochloric acid solution that adds 1M in the solution, after stirring 15h, with ultra-pure water sample is washed 4 times again, obtain boron doped graphene nanometer sheet;
Boron doped graphene nanometer sheet composite Ti O
2The preparation of photochemical catalyst
Boron doped graphene nanometer sheet is scattered in the ultra-pure water, and ultrasonic 1h adds gas phase titanium dioxide again, and mixed solution successively passes through ultrasonic 1h, and mechanical agitation 5h with 80 ℃ of lower oven dry of solution, grinds and obtains boron doped graphene nanometer sheet composite Ti O at last
2Photochemical catalyst, this boron doped graphene nanometer sheet composite Ti O
2Photocatalyst sheet has higher light induced electron ability and electron transport ability, therefore has high sunshine reduction CO
2Performance can be under solar light irradiation, with CO
2Be reduced into methane.Its photo-reduction CO
2Activity will be apparently higher than Graphene and graphene oxide composite Ti O
2Photochemical catalyst.
Claims (6)
1. boron doped graphene nanometer sheet composite Ti O
2The preparation method of photochemical catalyst is characterized in that, the method adopts cryogenic vacuum reduction and the ultrasonic preparation boron doped graphene nanometer sheet composite Ti O that combines take graphene oxide, gas phase titanium dioxide (P25) as presoma
2Photochemical catalyst specifically may further comprise the steps:
The preparation of boron doped graphene nanometer sheet
Measure the graphite oxide aqueous solution, be scattered in the ultra-pure water, behind the ultrasonic dispersion 1h, add again boric acid, 60 ℃ of lower evaporates to dryness behind the magnetic agitation 1h, sample behind the evaporate to dryness at 300 ℃ of lower vacuum reduction 3h, is scattered in the ultra-pure water, more ultrasonic 10h more again, in solution, add hydrochloric acid solution, after stirring 15h, with ultra-pure water sample is washed 4 times again, obtain boron doped graphene nanometer sheet;
Boron doped graphene nanometer sheet composite Ti O
2The preparation of photochemical catalyst
Boron doped graphene nanometer sheet is scattered in the ultra-pure water, and ultrasonic 1h adds gas phase titanium dioxide again, and mixed solution successively passes through ultrasonic 1h, and mechanical agitation 5h with 80 ℃ of lower oven dry of solution, grinds and obtains boron doped graphene nanometer sheet composite Ti O at last
2Photochemical catalyst.
2. a kind of boron doped graphene nanometer sheet composite Ti O according to claim 1
2The preparation method of photochemical catalyst is characterized in that, the concentration of described graphite oxide aqueous solution is 2-3mg/ml.
3. a kind of boron doped graphene nanometer sheet composite Ti O according to claim 1
2The preparation method of photochemical catalyst is characterized in that, the weight ratio of graphene oxide and boric acid is 0.01-0.015: 0.4.
4. a kind of boron doped graphene nanometer sheet composite Ti O according to claim 1
2The preparation method of photochemical catalyst is characterized in that, described graphite oxide aqueous solution adopts the Hummer method to prepare.
5. a kind of boron doped graphene nanometer sheet composite Ti O according to claim 1
2The preparation method of photochemical catalyst is characterized in that, the concentration of described hydrochloric acid solution is 1M.
6. a kind of boron doped graphene nanometer sheet composite Ti O according to claim 1
2The preparation method of photochemical catalyst is characterized in that, described boron doped graphene nanometer sheet composite Ti O
2Photochemical catalyst has high sunshine reduction CO
2Performance.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106492776A (en) * | 2016-11-02 | 2017-03-15 | 吉林大学 | One kind prepares TiO2The method of graphene composite material |
| CN107029694A (en) * | 2017-05-23 | 2017-08-11 | 中国石油大学(北京) | One kind doping carbon material and preparation method thereof |
| CN108640249A (en) * | 2018-03-21 | 2018-10-12 | 四川大学 | A method of sillenite bismuth ferrite catalysis persulfate is modified based on boron, neodymium and goes to remain incretion interferent in water removal |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102485647A (en) * | 2010-12-02 | 2012-06-06 | 中国科学院上海硅酸盐研究所 | Method for preparing boron doped graphene |
| CN102688755A (en) * | 2011-12-12 | 2012-09-26 | 湖南理工学院 | Ag/TiO2/graphene nanometer composite photocatalyst and preparation method thereof |
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2012
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102485647A (en) * | 2010-12-02 | 2012-06-06 | 中国科学院上海硅酸盐研究所 | Method for preparing boron doped graphene |
| CN102688755A (en) * | 2011-12-12 | 2012-09-26 | 湖南理工学院 | Ag/TiO2/graphene nanometer composite photocatalyst and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106492776A (en) * | 2016-11-02 | 2017-03-15 | 吉林大学 | One kind prepares TiO2The method of graphene composite material |
| CN107029694A (en) * | 2017-05-23 | 2017-08-11 | 中国石油大学(北京) | One kind doping carbon material and preparation method thereof |
| CN108640249A (en) * | 2018-03-21 | 2018-10-12 | 四川大学 | A method of sillenite bismuth ferrite catalysis persulfate is modified based on boron, neodymium and goes to remain incretion interferent in water removal |
| CN108640249B (en) * | 2018-03-21 | 2020-06-12 | 四川大学 | Method for removing residual endocrine disruptors in water based on boron and neodymium modified bismuthate ferrite catalysis persulfate |
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