CN103949234B - Boron doped graphene/TiO 2the preparation method of nanometer rods catalysis material - Google Patents
Boron doped graphene/TiO 2the preparation method of nanometer rods catalysis material Download PDFInfo
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Abstract
The invention provides a kind of boron doped graphene/TiO
2the preparation method of nanometer rods catalysis material, adopts method disclosed in American Chemical Society's " nanometer " periodical the 4th volume 4806-4814 page in 2010 to prepare graphene oxide; Take 8 ~ 80mg graphene oxide, add 15 ~ 25ml deionized water, ultrasonic disperse, obtain graphene oxide dispersion; In graphene oxide dispersion, add sodium borohydride and titanium trichloride solution, carry out hydro-thermal reaction after stirring, obtain sediment; After washing precipitate, vacuum drying, grinds to form uniform powder, obtains boron doped graphene/TiO
2nanometer rods composite photocatalyst material.This preparation method can make titanium dioxide well load on boron doped graphene, improve the photocatalytic activity of composite, chemisorbed is adsorbed with to pernicious gases such as nitric oxide nitrogen dioxide, is more conducive to the Adsorption and decomposition of pernicious gas at graphenic surface.
Description
Technical field
The invention belongs to nano-photocatalyst material technical field, relate to a kind of boron doped graphene/Rutile Type TiO
2the preparation method of nanometer rods composite photocatalyst material, obtains the catalysis material with high light catalytic activity with the one step hydro thermal method that preparation process is easy.
Background technology
Photocatalysis technology is the focus of current scientific research, and its range of application is very extensive, as sewage disposal, purification of air, Solar use, antibacterial, antifog and self-cleaning function etc.Titanium dioxide becomes a kind of desirable catalysis material because of its excellent photocatalysis performance, high activity, stability, nontoxic and low price, therefore may have great application prospect in energy regeneration and environmental protection.But the energy gap that titanium dioxide is large (Anatase 3.2eV, Rutile Type 3.0eV) makes it lower to the absorption efficiency of visible ray, hinder photo-generate electron-hole on generation so that affect photocatalytic process, so the photocatalysis of titanium dioxide in visible-range is restricted.Graphene is since being found, due to the photoelectric characteristic that it is very good, receive investigation and application widely, particularly there is important application in photocatalysis field, the introducing of Graphene makes system have higher pollutant adsorption capacity, the light abstraction width strengthened, the Charger transfer of enhancing and separating power.Wherein, boron doped graphene is compared to non-doped graphene: have higher electric conductivity, larger area load free charge density, stronger nitrogen oxide pernicious gas to adsorb (chemisorbed), if therefore by boron doped graphene and TiO
2compound, will have than non-doped graphene and TiO
2the separation rate of the photogenerated charge that composite is higher and stronger noxious pollutant adsorption-decomposition function.
The method preparing boron doped graphene mainly contains high-temperature hot doping method and chemical vapour deposition technique.Patent " doped graphene and preparation method thereof " (patent No. ZL200810113597.5, notification number CN101289181, day for announcing 2010.09.01) adopts chemical vapour deposition technique to prepare doped graphene, and underlayer temperature 500 ~ 1200 DEG C, needs catalyst.Patent application " a kind of preparation method and its usage of doped graphene " (application number 201010577424.6, publication No. CN102486993, date of publication 2012.06.06) make Graphene produce defect, 500 ~ 1000 DEG C of annealing in the atmosphere of doped chemical in disclosed preparation method.Patent application " a kind of doped graphene electrode material and preparation in macroscopic quantity methods and applications thereof " (application number 201110260849.9, publication No. CN102306781, date of publication 2012.01.04) under the high temperature conditions, pass into the Nitrogen element of variable concentrations or the atmosphere of boron element, realize the doping of the heteroatom of Graphene.Patent " preparation method of a kind of Graphene, doped graphene or graphene complex " (patent No. ZL201110306114.5, notification number CN102502593, day for announcing 2013.07.10) middle employing template, prepare doped graphene by chemical vapor deposition method or liquid-phase impregnation process.Patent application " boron doped graphene and preparation method thereof " (application number 201210137221.4, publication No. CN103382027, date of publication 2013.11.06) in disclosed method by silicon to 500 ~ 1300 DEG C in anaerobic room, in anaerobic reative cell, insufflation gas carbon source and gas boron source, make boron doped graphene.Patent application " a kind of boron doped graphene and preparation method thereof " (application number 201210171362.8, publication No. CN103449408, date of publication 2013.12.18) in graphite oxide is placed in the mist atmosphere that inert gas and boron source gas forms, 800 ~ 1100 DEG C of isothermal holding 0.5 ~ 2 hour, products therefrom is cooled to room temperature, obtains boron doped graphene.Patent application " preparation method of boron doped graphene " (application number 201210176572.6, publication No. CN103449415, date of publication 2013.12.18) substrate is positioned in disclosed method the reative cell of chemical vapor depsotition equipment, heating-up temperature is 500 ~ 1300 DEG C; Under protective gas atmosphere, alternately to passing into gaseous carbon source and gaseous boron source in described reative cell.Graphene and diboron trioxide is made to form mixture in patent application " preparation method of boron doped graphene " (application number 201210176590.4, publication No. CN103449416, date of publication 2013.12.18); Under argon atmosphere, described mixture is warming up to 700 ~ 1500 DEG C, cooling is purified, and obtains boron doped graphene.Graphene and diboron trioxide is made to form mixture in the disclosed method of patent application " preparation method of boron doped graphene " (application number 201210203203.1, publication No. CN103508440, date of publication 2014.01.15); Under the mixing atmosphere in protective gas and gaseous boron source, the environment temperature residing for described mixture is increased to 900 ~ 1100 DEG C, and keeps 0.5h ~ 3h, cool to room temperature, purify, obtain boron doped graphene.Patent application " nitrogen co-doped Graphene of a kind of boron and preparation method thereof " (application number 201210206950.0, publication No. CN103508445, date of publication 2014.01.15) get graphite oxide, urea and diboron trioxide by certain mass ratio in the method that provides and mix and be placed in reactor; Protective gas is passed in reactor; With the programming rate of 15 ~ 20 DEG C/min by the temperature to 800 in reactor ~ 900 DEG C, and keep 30min ~ 2h; Be be cooled to room temperature in the protective gas of 150 ~ 300ml/min at flow velocity, the obtained nitrogen co-doped Graphene of boron.Patent application " doping nitrogen or boron graphene/aluminum paper tinsel composite current collector, its preparation method, electrochemical electrode and electrochemical cell or capacitor " (application number 201210305295.4, publication No. CN103633333, date of publication 2014.03.12) in graphene oxide suspension is coated on aluminium foil, at 60 ~ 100 DEG C after drying, at BH
3/ H
2or NH
3/ H
2atmosphere in, 200 ~ 500 DEG C of reduction, prepare doped graphene.Carborundum high temperature thermal decomposition is prepared Graphene, doped with boron in wherein said carborundum in patent application " a kind of preparation method of boron doped graphene " (application number 201310556311.1, publication No. CN103613092, date of publication 2014.03.06).The common issue existed in above-mentioned prior art needs catalyst, template in preparation process, and the pickling in last handling process pollutes the environment, and complicated process of preparation, cost are higher.And consersion unit requires higher, needs to utilize mechanical pump, lobe pump and molecular pump that reative cell is pumped into oxygen-free environment, and needs by silicon to high temperature, preparation process power consumption is higher.Therefore, when preparing boron doped graphene and photocatalysis material of titanium dioxide with high-temperature hot doping method conventional at present and chemical vapour deposition technique, can only prepare with two-step method, patent application " a kind of boron doped graphene nanometer sheet composite Ti O
2the preparation method of photochemical catalyst " (application number 201210536358.7, publication No. CN102974333, date of publication 2013.03.20) disclose a kind of boron doped graphene nanometer sheet composite Ti O
2two one step preparation methods of photochemical catalyst, vacuum reduction is first adopted to prepare boron doped graphene nanometer sheet with the ultrasonic method combined, adopt ultrasonic mixing method again by P25 together with boron doped graphene nanometer sheet direct combination, two-step preparation makes preparation process comparatively complicated, preparation time is longer, and titanium dioxide can not well load be on Graphene, and the catalysis material in composite directly adopts commercial P25 titanium dioxide, and cost is higher.
Summary of the invention
The object of this invention is to provide boron doped graphene/TiO that a kind of technique is simple, with low cost
2the preparation method of nanometer rods catalysis material, can be carried on Graphene well by titanium dioxide.
For achieving the above object, the technical solution adopted in the present invention is: a kind of boron doped graphene/TiO
2the preparation method of nanometer rods catalysis material, with graphene oxide, sodium borohydride, titanium trichloride for presoma, adopts one step hydro thermal method to prepare boron doped graphene/Rutile Type TiO
2nanometer rods composite photocatalyst material, this preparation method specifically carries out according to the following steps:
Step 1: adopt method disclosed in American Chemical Society's " nanometer " periodical the 4th volume 4806-4814 page in 2010 to prepare graphene oxide;
Step 2: take 8 ~ 80mg graphene oxide, adds 15 ~ 25ml deionized water, ultrasonic disperse, obtains graphene oxide dispersion;
Step 3: add sodium borohydride and titanium trichloride solution in graphene oxide dispersion, carries out hydro-thermal reaction after stirring, obtains sediment;
Step 4: after washing precipitate, vacuum drying, grinds to form uniform powder, obtains boron doped graphene/TiO
2nanometer rods composite photocatalyst material.
The inventive method, using sodium borohydride and titanium trichloride as raw material, adopts one step hydro thermal method to prepare boron doped graphene/TiO
2nanometer rod composite material, titanium dioxide can load on boron doped graphene, make the photocatalytic activity of this composite far above commercial titanium dioxide well.And because boron doped graphene is compared to non-doped graphene: there are higher electric conductivity and area load free charge density; Chemisorbed is adsorbed with to pernicious gases such as nitric oxide nitrogen dioxide, is more conducive to the Adsorption and decomposition of pernicious gas at graphenic surface, therefore boron doped graphene/TiO
2the degraded of nanometer rods composite photocatalyst material in pernicious gas and pollutant is better than non-doped graphene/TiO
2composite.
Accompanying drawing explanation
Fig. 1 is boron doped graphene/Rutile Type TiO that embodiment 1 obtains
2the X-ray diffraction spectrogram of nanometer rods composite photocatalyst material.
Fig. 2 is boron doped graphene/Rutile Type TiO that embodiment 1 obtains
2the scanning electron micrograph of nanometer rods composite photocatalyst material.
Fig. 3 is boron doped graphene/Rutile Type TiO that embodiment 1 obtains
2the transmission electron micrograph of nanometer rods composite photocatalyst material.
Fig. 4 is boron doped graphene/Rutile Type TiO that embodiment 1 obtains
2the high-resolution transmission electron micrograph of nanometer rods composite photocatalyst material.
Fig. 5 is boron doped graphene/Rutile Type TiO that embodiment 1 obtains
2the absorption spectrum of nanometer rods composite photocatalyst material.
Fig. 6 is the transmission electron micrograph of the boron doped graphene that comparative example 1 obtains.
Fig. 7 is the x-ray photoelectron power spectrum of the boron doped graphene that comparative example 1 obtains.
Fig. 8 is the Raman spectrum of the boron doped graphene that comparative example 1 obtains.
Fig. 9 is the photocatalytic degradation effect figure of embodiment 1, comparative example 2 and commercial P25.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Boron doped graphene/TiO of the present invention
2the preparation method of nanometer rods composite photocatalyst material for presoma, adopts one step hydro thermal method to prepare boron doped graphene/Rutile Type TiO with graphene oxide, sodium borohydride, titanium trichloride
2nanometer rods composite photocatalyst material.This preparation method specifically carries out according to the following steps:
Step 1: adopt American Chemical Society's " nanometer " periodical the 4th volume 4806-4814 page (ACSNano.2010,4 (8): 4806-4814) disclosed method in 2010 to prepare graphene oxide (GO);
Step 2: take 8 ~ 80mg graphene oxide, adds 15 ~ 25ml deionized water, and ultrasonic disperse 0.5 ~ 1 hour, obtains graphene oxide dispersion;
Step 3: add 0.3 ~ 0.9g sodium borohydride and 3.38 ~ 13.52mL mass percent concentration is the titanium trichloride solution of 20% in graphene oxide dispersion, sodium borohydride is as boron source and reducing agent, and titanium trichloride is as titanium source; Magnetic stirring apparatus stirs 30 ~ 50min, then ultrasonic agitation 30 ~ 50min, finally proceed in water heating kettle by solution, at the temperature of 160 ~ 200 DEG C, hydro-thermal reaction 12 ~ 16 hours, obtains sediment;
Step 4: by sediment successively with after deionized water and ethanol difference centrifuge washing, vacuum drying 8 ~ 12 hours at the temperature of 50 ~ 70 DEG C, then grind to form uniform powder with agate mortar, obtain boron doped graphene/TiO
2nanometer rods composite photocatalyst material, this composite photocatalyst material is boron doped graphene/Rutile Type TiO
2nanometer rods composite photocatalyst material..
Due to prior art Problems existing, when making to prepare highly active boron doped graphene titanic oxide composite photochemical catalyst material, one-step method can only be adopted, and reaction temperature can not be high.Patent " a kind of preparation method of boron doped graphene " (patent No. ZL201010570879.5, notification number CN102485647, day for announcing 2013.10.30) disclose a kind of preparation method of boron doped graphene, active metal and low-carbon (LC) halogenated hydrocarbons, boron source is utilized to react, in-situ boron doped graphene is realized under special reaction condition, but this reaction system is water-less environment, even if add titanium source can not react generation titanium dioxide.Patent application " boron doped graphene-polyaniline nano compound and preparation method thereof " (application number 201310149975.6) discloses a kind of preparation method of boron doped graphene, graphite oxide is placed in water ultrasonic disperse, boric acid is added Hydrothermal Synthesis in this mixed liquor, the boron doped graphene of this kind of method synthesis is of low quality, because this system take water as solvent, take boric acid as boron source, there is no adding of reducing agent, therefore the oxygen-containing functional group in graphene oxide can not reduce substantially, and the essence of generation is boron doped redox graphene.The disclosed boron doped graphene of patent application " tin ash/boron doped graphene nano-complex and preparation method thereof " (application number 20130313571.6) is placed in the mixed solution ultrasonic disperse of water and ethanol with graphite oxide, boric acid is as boron source, therefore the oxygen-containing functional group in graphene oxide can not reduce substantially, and boron doped graphene and tin ash compound, mainly consider its application in energy field and other field of electronic devices.High temperature time prepared by one-step method can make the titanium dioxide optical catalyst reunion phase transformation prepared, and then significantly reduces the photocatalytic activity of material.
Consider the importance of catalysis material in the energy and environment etc. and the limitation of above prior art, preparation method of the present invention adopts one step hydro thermal method to prepare boron doped graphene Rutile Type TiO
2nanometer rods composite photocatalyst material, make titanium dioxide can well load on boron doped graphene, this is because: after hydro-thermal reaction starts, the titanium source in system is hydrolyzed in surface of graphene oxide, then forms nucleus gradually, and the growth of crystal grain occurs; Simultaneous oxidation Graphene carries out the reduction of the graphene-doped skeleton of boron and graphene oxide.And in the growth course of titania, the carbon in the graphene oxide during the titanium in titanium dioxide and oxygen can adulterate with reduction forms the chemical bond of titanium-oxygen-carbon.Therefore compared to the mixing of two-step method, titanium dioxide is made firmly to be attached to boron doped graphene surface (because general attachment is adhered to intermolecular force between the two in one-step method process, and be chemical bond herein, adhere to more secure rigid), adhere to closely and be more conducive to leading away light induced electron, reduce the recombination rate of photo-generate electron-hole, improve photocatalytic activity.And in the process of growth, carbon in boron doped graphene can be formed in the preparation method chemical of the present invention of titanium-oxygen-carbon with the titania in growth, using sodium borohydride and titanium trichloride as raw material, while carrying boron source nitrogenous source, because of both stronger reducing agent, therefore fully graphene oxide can be reduced into Graphene, and complete the doping of boron: the high-temperature and high-pressure conditions of hydro-thermal reaction, boron source sodium borohydride is decomposed, form a sufficient boron source atmosphere, and in the reduction process of graphene oxide, boron atom can form BC with the carbon atom in graphene oxide
3and BC
2the structures such as O, and then make boron doping enter Graphene skeleton, and why boron is not doped into titanium dioxide in the nano-complex that patent application " tin ash/boron doped graphene nano-complex and preparation method thereof " provides, that therefore boron more difficult Substitute For Partial oxygen doping in the crystallization process of titanium dioxide enters crystal because the atomic radius of boron and oxygen and electronegativity differ comparatively large.Present invention applicant, on the basis of great many of experiments, has summed up the condition that can generate monodimension nano stick pattern titanium dioxide, i.e. the reaction condition that provides of preparation method of the present invention.Because the consumption of reaction time, reaction temperature and titanium trichloride is the key factor affecting titanium dioxide pattern, prove by experiment, if do not reacted in the scope of reaction time disclosed in preparation method of the present invention, reaction temperature and titanium trichloride consumption, just can not generate nano bar-shape structure, or the nanometer rods pattern heterogeneity generated.Preparation method of the present invention can make titanium dioxide well load on Graphene, boron doping can be realized, and obtain the advantage of Rod-like shape, because, the appearance and size of titanium dioxide has important impact to its character and application, nanorod structure has higher specific area compared to multidimensional nanostructured, and owing to can above moving in dimension direction (direction of rod) and have lower photo-generate electron-hole recombination rate in light induced electron and hole, therefore photocatalytic activity be higher.So the composite adopting preparation method of the present invention to obtain has very strong photocatalytic activity.And the method equipment used is simple, operation simple and feasible, without the need to additionally using metallic catalyst, production cost is low, can be used for batch production.
embodiment 1
Method disclosed in American Chemical Society's " nanometer " periodical the 4th volume 4806-4814 page in 2010 is adopted to prepare graphene oxide (GO); Take 80mg graphene oxide, add 25ml deionized water, ultrasonic disperse 1 hour, obtains graphene oxide dispersion; In graphene oxide dispersion, add 0.3g sodium borohydride and 8.45mL mass percent concentration is the titanium trichloride solution of 20%, sodium borohydride is as boron source and reducing agent, and titanium trichloride is as titanium source; Magnetic stirring apparatus stirs 30min, then ultrasonic agitation 40min, finally proceed in water heating kettle by solution, at the temperature of 180 DEG C, hydro-thermal reaction 14 hours, obtains sediment; Successively with after deionized water and ethanol difference centrifuge washing sediment, vacuum drying 10 hours at the temperature of 60 DEG C, then grind to form uniform powder with agate mortar, obtain boron doped graphene/TiO
2nanometer rods composite photocatalyst material.This boron doped graphene/TiO
2as shown in Figure 1, as can be seen from Figure 1, the sample of preparation is the good Rutile Type of crystallinity to the X-ray diffraction of nanometer rods composite photocatalyst material.Fig. 2 is the scanning electron micrograph preparing sample, and red schorl phase titanium dioxide is all the nanometer rods of about 140nm as we know from the figure, and pattern is comparatively even.Fig. 3 is the transmission electron microscope figure preparing sample, as we know from the figure, and TiO
2be dispersed on the Graphene of individual layer preferably, and the titanium dioxide pattern of Rutile Type is length is about 140nm, diameter is the nanometer rods of about 20nm.Fig. 4 is TEM and the HRTEM photo preparing sample, as can be seen from HRTEM photo, adjacent fringe spacing 3.24 can be summed up as (110) crystal face of Rutile Type, and as we know from the figure, sample is the good nanometer rods of crystallinity along the growth of [001] direction.Fig. 5 is the absorption spectrum of sample, and the ABSORPTION EDGE of sample is greatly about about 410nm as we know from the figure.
comparative example 1
Adopt document ACSNano.2010, disclosed in 4 (8): 4806-4814, method prepares graphene oxide; Take the graphene oxide of 80mg, add 25mL deionized water, ultrasonic disperse 1 hour, obtain GO dispersion liquid, add 0.3g sodium borohydride subsequently as boron source and reducing agent, magnetic stirring apparatus stirs 30min, ultrasonic 40min again, finally solution is proceeded in 50mL water heating kettle, hydro-thermal reaction 14 hours at the temperature of 180 DEG C, after the sediment obtained being used successively deionized water and ethanol difference centrifuge washing, vacuum drying 10 hours at the temperature of 60 DEG C, grind to form uniform powder with agate mortar again, obtain boron doped graphene.The transmission electron microscope photo of this boron doped graphene as shown in Figure 6, as can be known from Fig. 6, the boron doped graphene of preparation shows some sizes at micron-sized thin slice, observes the fold of graphene platelet simultaneously, shows that boron doped graphene sample is made up of few layer graphene sheet.As shown in Figure 7, Fig. 7 boron 1S spectrum shows the XPS spectrum of this boron doped graphene, and boron element is effectively mixed with in Graphene, and learns after the matching to boron 1S, and boron element exists with the structure of BC3 and BC2O in Graphene.As shown in Figure 8, as we know from the figure, compared to unadulterated Graphene, boron doped graphene has a larger I to the Raman spectrum of this boron doped graphene
d/ I
g, confirmed the doping of boron element in Graphene further.
comparative example 2
Adopt document ACSNano.2010, disclosed in 4 (8): 4806-4814, method prepares graphene oxide; Take 60mg graphene oxide, add the deionized water of 25mL, ultrasonic disperse 1 hour, obtain GO dispersion liquid, adding 6.76mL mass percent concentration is that the titanium trichloride of 20% is as titanium source, magnetic stirring apparatus stirs 30min, ultrasonic 40min again, finally solution is proceeded in 50mL water heating kettle, hydro-thermal reaction 14 hours at the temperature of 180 DEG C, after the sediment obtained being used successively deionized water and ethanol difference centrifuge washing, vacuum drying 10 hours at 60 DEG C of temperature, grind to form uniform powder with agate mortar again, obtain boron doped graphene/Rutile Type TiO
2nanometer rods composite photocatalyst material.
the sign of photocatalysis effect:
By to NO
xthe oxidation reaction of gas carries out photocatalytic activity sign, and the biodegrading process of NOR with reference to the JIS standard that Japanese Industrial Standards Committee formulated in January, 2004.The Main Function of catalysis material is that NO gas oxygen is changed into HNO
2and HNO
3deng.In this experiment, the mist (volumetric mixture ratio is 1 ︰ 1) of the NO of 1ppm and air is continuously passed into and is equipped with in the shading closed reactor of photochemical catalyst, when illumination, NO is oxidized, by measuring from the NO concentration reactor effluent air, NO concentration before and after contrast illumination obtains its resolution ratio, thus realizes the evaluation of the catalytic activity of this photochemical catalyst.The concentration of NO gas adopts YanacoELC-88A type NO
xanalysis-e/or determining, light source uses high-pressure sodium lamp.Use simultaneously and there is the commercial powder of highly active titanium dioxide (P-25, German Degussa company produce) as reference sample.Concrete characterizing method is as follows: powder sample being filled into one piece of area is in the middle of the sample cell of 20 × 15 × 0.5mm, and being fixed to a volume is 373cm
3closed reactor in.Respectively the NO Standard Gases of 100mL and the dry air of 100mL being passed into volume is in the glass gas cylinder of 200mL, by being mixed to get the NO/Air mist (NO concentration is 1ppm) of 200mL fully.When not having illumination, the NO gas uniform speed of above-mentioned 1ppm passes in reactor by (dark condition), and makes it reach stable state.Using the high-pressure sodium lamp of 450W as light source irradiation sample, to the evaluation of the photocatalytic activity of NO gas.As can be seen from Figure 9, compared to commercial P25 and non-doped graphene photocatalysis material of titanium dioxide, boron doped graphene/Rutile Type TiO that embodiment 1 is obtained
2nanometer rods composite photocatalyst material has the strongest nitrogen oxide degradation capability.
embodiment 2
Adopt document ACSNano.2010, disclosed in 4 (8): 4806-4814, method prepares graphene oxide, take 40mg graphene oxide, add 20mL deionized water, ultrasonic disperse 0.75 hour, obtain graphene oxide dispersion, add 0.61g sodium borohydride subsequently and 3.38mL mass percent concentration is the titanium trichloride solution of 20%, magnetic stirring apparatus stirs 40min, ultrasonic agitation 30min again, finally solution is proceeded in 50mL water heating kettle, hydro-thermal reaction 16 hours at 160 DEG C of temperature, after the sediment obtained being used successively deionized water and ethanol difference centrifuge washing, vacuum drying 12 hours at 50 DEG C of temperature, uniform powder is ground to form again with agate mortar, obtain boron doped graphene/Rutile Type TiO
2nanometer rods composite photocatalyst material.
embodiment 3
Adopt document ACSNano.2010, disclosed in 4 (8): 4806-4814, method prepares graphene oxide, take 8mg graphene oxide, add 15mL deionized water, ultrasonic disperse 0.5 hour, obtain graphene oxide dispersion, add 0.9g sodium borohydride subsequently and 13.52mL mass percent concentration is the titanium trichloride solution of 20%, magnetic stirring apparatus stirs 50min, ultrasonic agitation 50min again, finally solution is proceeded in 50mL water heating kettle, hydro-thermal reaction 12 hours at 200 DEG C of temperature, after the sediment obtained being used successively deionized water and ethanol difference centrifuge washing, vacuum drying 8 hours at 70 DEG C of temperature, uniform powder is ground to form again with agate mortar, obtain boron doped graphene/Rutile Type TiO
2nanometer rods composite photocatalyst material.
Claims (2)
1. boron doped graphene/TiO
2the preparation method of nanometer rods catalysis material, with graphene oxide, sodium borohydride, titanium trichloride for presoma, adopts one step hydro thermal method to prepare boron doped graphene/Rutile Type TiO
2nanometer rods composite photocatalyst material, is characterized in that, this preparation method specifically carries out according to the following steps:
Step 1: adopt method disclosed in American Chemical Society's " nanometer " periodical the 4th volume 4806-4814 page in 2010 to prepare graphene oxide;
Step 2: take 8 ~ 80mg graphene oxide, adds 15 ~ 25mL deionized water, ultrasonic disperse, obtains graphene oxide dispersion;
Step 3: add 0.3 ~ 0.9g sodium borohydride and 3.38 ~ 13.52mL mass percent concentration is the titanium trichloride solution of 20% in graphene oxide dispersion, after stirring, at the temperature of 160 ~ 200 DEG C, hydro-thermal reaction 12 ~ 16 hours, obtains sediment;
Step 4: after washing precipitate, vacuum drying, grinds to form uniform powder, obtains boron doped graphene/TiO
2nanometer rods composite photocatalyst material.
2. boron doped graphene/TiO according to claim 1
2the preparation method of nanometer rods catalysis material, is characterized in that, in described step 4, by sediment successively with after deionized water and ethanol difference centrifuge washing, and vacuum drying 8 ~ 12 hours at the temperature of 50 ~ 70 DEG C.
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| CN114643050B (en) * | 2022-05-19 | 2022-08-23 | 浙江晟格生物科技有限公司 | Composite catalyst for improving lactose isomerization yield, preparation method and application |
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| CN102437321B (en) * | 2011-12-20 | 2013-10-16 | 中国科学院新疆理化技术研究所 | Graphene-TiO2(B) nanotube composite material and preparation method thereof |
| KR20130134123A (en) * | 2012-05-30 | 2013-12-10 | 한국과학기술연구원 | Boron-doped reduction graphine of adjusting physical properties of semiconductor and electric conductivity, and preparation thereof |
| CN102728337B (en) * | 2012-06-08 | 2014-04-30 | 华北电力大学 | Graphite / titanium dioxide composite material and preparation method thereof |
| CN102976314B (en) * | 2012-11-29 | 2015-05-13 | 中国科学院宁波材料技术与工程研究所 | Novel titanium dioxide-graphene nano-composite material as well as manufacturing method and application thereof |
| CN103372428B (en) * | 2013-05-10 | 2015-01-21 | 南昌大学 | Preparation method of nitrogen-doped graphene loaded platinum nano-particle catalyst |
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