CN103949234A - Preparation method of boron-doped graphene/TiO2 nanorod photocatalytic material - Google Patents
Preparation method of boron-doped graphene/TiO2 nanorod photocatalytic material Download PDFInfo
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Abstract
The invention provides a preparation method of boron-doped graphene/TiO2 nanorod photocatalytic material. The method comprises the following steps of preparing graphene oxide by a method disclosed in pages from 4806 to 4814 in the volume 4 in 2010 of nanometer periodical of the American chemical society; weighing 8-80mg of graphene oxide, feeding 15-25ml of deionized water and carrying out ultrasonic dispersion to obtain graphene oxide dispersion liquid; feeding sodium borohydride and titanium trichloride solution into the graphene oxide dispersion liquid, stirring and then carrying out a hydrothermal reaction to obtain precipitate; and washing the precipitate, carrying out vacuum drying, and grinding the product into uniform powder to obtain the boron-doped graphene/TiO2 nanorod composite photocatalytic material. After the method is adopted, titanium dioxide can be well loaded on boron-doped graphene, the photocatalytic activity of the composite material is improved, harmful gases such as nitrogen oxide and nitrogen dioxide can be chemically adsorbed, and the harmful gases can be well adsorbed and decomposed on the surface of the graphene.
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, makes the catalysis material with high light catalytic activity with the easy one step hydro thermal method of preparation process.
Background technology
Photocatalysis technology is the focus of current scientific research, and its range of application is very extensive, as sewage disposal, air cleaning, solar energy utilization, antibacterial, antifog and self-cleaning function etc.Titanium dioxide, because its good photocatalysis performance, high activity, stability, nontoxic and low price become a kind of desirable catalysis material, therefore may have great application prospect aspect 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, hindered light induced 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 its very good photoelectric characteristic, be subject to studying widely and applying, particularly in photocatalysis field, there is important application, the introducing of Graphene makes system have higher pollutant adsorption capacity, the light abstraction width strengthening, the electric charge of enhancing shifts and separating power.Wherein, boron doped graphene is than doped graphene not: have higher electric conductivity, larger area load free charge density, stronger nitrogen oxide pernicious gas absorption (chemisorbed), if therefore by boron doped graphene and TiO
2compound, will have than not doped graphene and TiO
2the separation rate of the photogenerated charge that composite is higher and stronger noxious pollutant adsorption-decomposition function.
The method of 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) adopt chemical vapour deposition technique to prepare doped graphene, 500～1200 ℃ of underlayer temperatures, need catalyst.The preparation method and its usage > > (application number 201010577424.6 of a patent application < < doped graphene, publication No. CN102486993, date of publication 2012.06.06) in disclosed preparation method, make Graphene produce defect, 500～1000 ℃ of annealing in the atmosphere of doped chemical.Patent application < < doped graphene electrode material and preparation in macroscopic quantity methods and applications > > (application number 201110260849.9 thereof, publication No. CN102306781, date of publication 2012.01.04) under hot conditions, the atmosphere that passes into Nitrogen element or the boron element of variable concentrations, realizes the doping of the heteroatom of Graphene.The preparation method > > (patent No. ZL201110306114.5 of patent < < a Graphene, doped graphene or graphene complex, notification number CN102502593, day for announcing 2013.07.10) in, adopt template, by chemical vapor deposition method or liquid impregnation method, prepare doped graphene.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, the substrate in anaerobic chamber is heated to 500～1300 ℃, in anaerobic reative cell, be filled with gaseous carbon sources and gas boron source, make boron doped graphene.A patent application < < 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 to the mist atmosphere that inert gas and boron source gas form, 800～1100 ℃ of insulations are processed 0.5～2 hour, products therefrom is cooled to room temperature, obtains boron doped graphene.The preparation method > > (application number 201210176572.6 of patent application < < boron doped graphene, publication No. CN103449415, date of publication 2013.12.18) in disclosed method, substrate is positioned over to the reative cell of chemical vapor depsotition equipment, heating-up temperature is 500～1300 ℃; Under protective gas atmosphere, alternately in described reative cell, pass into gaseous carbon source and gaseous boron source.The preparation method > > (application number 201210176590.4 of patent application < < boron doped graphene, publication No. CN103449416, date of publication 2013.12.18) in, make Graphene and diboron trioxide form mixture; Under argon atmosphere, described mixture is warming up to 700～1500 ℃, cooling purification, obtains boron doped graphene.The preparation method > > (application number 201210203203.1 of patent application < < boron doped graphene, publication No. CN103508440, date of publication 2014.01.15) in disclosed method, make Graphene and diboron trioxide form mixture; Under the mixing atmosphere in protective gas and gaseous boron source, the residing environment temperature of described mixture is increased to 900～1100 ℃, and keeps 0.5h～3h, cool to room temperature, purifies, and obtains boron doped graphene.The patent application < < nitrogen co-doped Graphene of boron and preparation method thereof > > (application number 201210206950.0, publication No. CN103508445, date of publication 2014.01.15) in the method providing, by certain mass ratio, getting graphite oxide, urea and diboron trioxide mixes and is placed in reactor; In reactor, pass into protective gas; Programming rate with 15～20 ℃/min is warming up to 800～900 ℃ by the temperature in reactor, and keeps 30min～2h; In the protective gas that is 150～300ml/min at flow velocity, be cooled to room temperature, make the 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, after dry at 60～100 ℃, at BH
3/ H
2or NH
3/ H
2atmosphere in, 200～500 ℃ of reduction, prepare doped graphene.The preparation method > > (application number 201310556311.1 of a patent application < < boron doped graphene, publication No. CN103613092, date of publication 2014.03.06) in, the thermal decomposition of carborundum high temperature is prepared to Graphene, in wherein said carborundum doped with boron.The common issue existing in above-mentioned prior art is in preparation process, to need catalyst, template, and the pickling in last handling process pollutes the environment, and complicated process of preparation, cost are higher.And consersion unit has relatively high expectations, need to utilize mechanical pump, lobe pump and molecular pump that reative cell is pumped into oxygen-free environment, and substrate need to be heated to high temperature, preparation process power consumption is higher.Therefore, while preparing boron doped graphene and photocatalysis material of titanium dioxide with conventional at present high temperature hot doping method and chemical vapour deposition technique, can only prepare with two-step method patent application < < 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) has announced a kind of boron doped graphene nanometer sheet composite Ti O
2two one step preparation methods of photochemical catalyst, first adopt vacuum reduction to prepare boron doped graphene nanometer sheet with the ultrasonic method combining, adopt again ultrasonic mixing method 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 on Graphene, and the catalysis material in composite is directly to adopt commercial P25 titanium dioxide, and cost is higher.
Summary of the invention
The object of this invention is to provide a kind of technique boron doped graphene/TiO simple, with low cost
2the preparation method of nanometer rods catalysis material, can be carried on titanium dioxide on Graphene well.
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, take graphene oxide, sodium borohydride, titanium trichloride is 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 the < < of the American Chemical Society nanometer > > periodical disclosed method of the 4th volume 4806-4814 page in 2010 to prepare graphene oxide;
Step 2: take 8～80mg graphene oxide, add 15～25ml deionized water, ultrasonic dispersion, obtains graphene oxide dispersion liquid;
Step 3: add sodium borohydride and titanium trichloride solution in graphene oxide dispersion liquid, carry out hydro-thermal reaction after stirring, obtain 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 is usingd 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 well, makes the photocatalytic activity of this composite far above commercial titanium dioxide.And because boron doped graphene is than doped graphene not: have higher electric conductivity and area load free charge density; Absorption to pernicious gases such as nitric oxide nitrogen dioxide has chemisorbed, is more conducive to pernicious gas at the Adsorption and decomposition on Graphene surface, so boron doped graphene/TiO
2nanometer rods composite photocatalyst material is better than not doped graphene/TiO in the degraded aspect pernicious gas and pollutant
2composite.
Accompanying drawing explanation
Fig. 1 is boron doped graphene/Rutile Type TiO that embodiment 1 makes
2the X-ray diffraction spectrogram of nanometer rods composite photocatalyst material.
Fig. 2 is boron doped graphene/Rutile Type TiO that embodiment 1 makes
2the scanning electron micrograph of nanometer rods composite photocatalyst material.
Fig. 3 is boron doped graphene/Rutile Type TiO that embodiment 1 makes
2the transmission electron micrograph of nanometer rods composite photocatalyst material.
Fig. 4 is boron doped graphene/Rutile Type TiO that embodiment 1 makes
2the high-resolution transmission electron micrograph of nanometer rods composite photocatalyst material.
Fig. 5 is boron doped graphene/Rutile Type TiO that embodiment 1 makes
2the absorption spectrum of nanometer rods composite photocatalyst material.
Fig. 6 is the transmission electron micrograph of the boron doped graphene that makes of comparative example 1.
Fig. 7 is the x-ray photoelectron power spectrum of the boron doped graphene that makes of comparative example 1.
Fig. 8 is the Raman spectrum of the boron doped graphene that makes of comparative example 1.
Fig. 9 is the photocatalytic degradation design sketch of embodiment 1, comparative example 2 and commercial P25.
The specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Boron doped graphene/TiO of the present invention
2it is presoma that the preparation method of nanometer rods composite photocatalyst material be take graphene oxide, sodium borohydride, titanium trichloride, 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: (ACS Nano. 2010,4 (8): 4806-4814) disclosed method is prepared graphene oxide (GO) to adopt the < < of American Chemical Society nanometer > > periodical the 4th volume 4806-4814 page in 2010;
Step 2: take 8～80mg graphene oxide, add 15～25ml deionized water, ultrasonic dispersion 0.5～1 hour, obtains graphene oxide dispersion liquid;
Step 3: add the titanium trichloride solution that 0.3～0.9g sodium borohydride and 3.38～13.52mL mass percent concentration are 20% in graphene oxide dispersion liquid, sodium borohydride is as boron source and reducing agent, and titanium trichloride is as titanium source; On magnetic stirring apparatus, stir 30～50min, then ultrasonic agitation 30～50min, finally solution is proceeded in water heating kettle, at the temperature of 160～200 ℃, hydro-thermal reaction 12～16 hours, obtains sediment;
Step 4: successively with after deionized water and ethanol difference centrifuge washing, vacuum drying is 8～12 hours at the temperature of 50～70 ℃, then grinds to form uniform powder with agate mortar, obtains boron doped graphene/TiO by sediment
2nanometer rods composite photocatalyst material, this composite photocatalyst material is boron doped graphene/Rutile Type TiO
2nanometer rods composite photocatalyst material..
Problem because prior art exists, while making to prepare highly active boron doped graphene titanic oxide composite photochemical catalyst material, can only adopt one-step method, and reaction temperature can not be high.The preparation method > > (patent No. ZL201010570879.5 of a patent < < boron doped graphene, notification number CN102485647, day for announcing 2013.10.30) a kind of preparation method of boron doped graphene is disclosed, utilize active metal to react with low-carbon (LC) halogenated hydrocarbons, boron source, under special reaction condition, realize in-situ boron doped graphene, 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) has announced a kind of preparation method of boron doped graphene, graphite oxide is placed in to the ultrasonic dispersion of water, boric acid is added to Hydrothermal Synthesis in this mixed liquor, the synthetic boron doped graphene of this kind of method is of low quality, because this system be 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, the essence generating is boron doped redox graphene.Patent application < < tin ash/boron doped graphene nano-complex and preparation method thereof the disclosed boron doped graphene of > > (application number 20130313571.6) is placed in the ultrasonic dispersion of mixed solution 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, be mainly to consider its application in energy field and other field of electronic devices.High temperature when prepared by one-step method can make the titanium dioxide optical catalyst reunion phase transformation of preparation, and then significantly reduces the photocatalytic activity of material.
Consider that catalysis material is in the importance of the aspects such as the energy and environment 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, can load on boron doped graphene titanium dioxide well, this be because: after hydro-thermal reaction starts, the titanium source in system, at graphene oxide surface hydrolysis, then forms gradually nucleus, 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 than the mixing of two-step method, in one-step method process, make titanium dioxide firmly be attached to boron doped graphene surface (because general adhering to is to adhere to intermolecular force between the two, and be chemical bond herein, adhere to more firm tight), adhere to closely and be more conducive to lead away light induced electron, reduce the recombination rate in light induced electron hole, improve photocatalytic activity.And in the process of growth, carbon in boron doped graphene can with growth in titania form in the preparation method chemical of the present invention of titanium-oxygen-carbon, using sodium borohydride and titanium trichloride as raw material, when carrying boron source nitrogenous source, because of both stronger reducing agent, therefore can fully graphene oxide 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 with graphene oxide in carbon atom form BC
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, be because atomic radius and the electronegativity of boron and oxygen differ larger, so boron more difficult Substitute For Partial oxygen doping in the crystallization process of titanium dioxide enter crystal.The present patent application people, on the basis of great many of experiments, has summed up the condition that can generate monodimension nano stick pattern titanium dioxide, the reaction condition that preparation method of the present invention provides.Because the consumption of reaction time, reaction temperature and titanium trichloride is the key factor that affects titanium dioxide pattern, prove by experiment, if do not reacted in the scope of disclosed reaction time of 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 generating.Preparation method of the present invention can make titanium dioxide load on well on Graphene, can realize boron doping, 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 than multidimensional nanostructured, and because can mobilely there be lower light induced electron hole-recombination rate in light induced electron and hole dimension direction (direction of rod) is upper, so photocatalytic activity is higher.So the composite that adopts preparation method of the present invention to make has very strong photocatalytic activity.And the method equipment used is simple, operation simple and feasible, without the extra metallic catalyst that uses, production cost is low, can be used for batch production.
embodiment 1
Adopt the < < of the American Chemical Society nanometer > > periodical disclosed method of the 4th volume 4806-4814 page in 2010 to prepare graphene oxide (GO); Take 80mg graphene oxide, add 25ml deionized water, ultrasonic dispersion 1 hour, obtains graphene oxide dispersion liquid; In graphene oxide dispersion liquid, add the titanium trichloride solution that 0.3g sodium borohydride and 8.45mL mass percent concentration are 20%, sodium borohydride is as boron source and reducing agent, and titanium trichloride is as titanium source; On magnetic stirring apparatus, stir 30min, then ultrasonic agitation 40min, finally solution is proceeded in water heating kettle, at the temperature of 180 ℃, hydro-thermal reaction 14 hours, obtains sediment; With after deionized water and ethanol difference centrifuge washing sediment, at the temperature of 60 ℃, vacuum drying is 10 hours, then grinds to form uniform powder with agate mortar, obtains boron doped graphene/TiO successively
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 of preparing sample, and red schorl phase titanium dioxide is all the nanometer rods of 140nm left and right as we know from the figure, and pattern is comparatively even.Fig. 3 is the transmission electron microscope figure for preparing sample, as we know from the figure, and TiO
2be dispersed in preferably on the Graphene of individual layer, and the titanium dioxide pattern of Rutile Type is that length is that 140nm left and right, diameter are the nanometer rods of 20nm left and right.Fig. 4 is TEM and the HRTEM photo of preparing sample, from HRTEM photo, can find out, 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 410nm left and right as we know from the figure.
comparative example 1
Adopt document ACS Nano. 2010,4 (8): the disclosed method of 4806-4814 is prepared graphene oxide; Take the graphene oxide of 80mg, add 25mL deionized water, ultrasonic dispersion 1 hour, obtain GO dispersion liquid, add subsequently 0.3g sodium borohydride as boron source and reducing agent, on magnetic stirring apparatus, stir 30min, ultrasonic 40min again, finally solution is proceeded in 50mL water heating kettle, at the temperature of 180 ℃, hydro-thermal reaction is 14 hours, and by the sediment obtaining, successively with after deionized water and ethanol difference centrifuge washing, at the temperature of 60 ℃, vacuum drying is 10 hours, with agate mortar, grind to form uniform powder 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 has shown that some sizes, at micron-sized thin slice, observe the fold of graphene platelet simultaneously, shows that boron doped graphene sample is comprised 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 has effectively mixed in Graphene, and through to learning after the matching of boron 1S, boron element exists with the structure of BC3 and BC2O in Graphene.As shown in Figure 8, as we know from the figure, than unadulterated Graphene, boron doped graphene has a larger I to the Raman spectrum of this boron doped graphene
d/ I
g, further confirmed the doping of boron element in Graphene.
comparative example 2
Adopt document ACS Nano. 2010,4 (8): the disclosed method of 4806-4814 is prepared graphene oxide; Take 60mg graphene oxide, the deionized water that adds 25mL, ultrasonic dispersion 1 hour, obtain GO dispersion liquid, adding 6.76mL mass percent concentration is that 20% titanium trichloride is as titanium source, on magnetic stirring apparatus, stir 30min, ultrasonic 40min again, finally solution is proceeded in 50mL water heating kettle, at the temperature of 180 ℃, hydro-thermal reaction is 14 hours, and by the sediment obtaining, successively with after deionized water and ethanol difference centrifuge washing, at 60 ℃ of temperature, vacuum drying is 10 hours, with agate mortar, grind to form uniform powder 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 is carried out photocatalytic activity sign, the JIS standard that the biodegrading process of NOR is formulated in January, 2004 with reference to Japanese Industrial Standards Committee.The Main Function of catalysis material is that NO gas oxygen is changed into HNO
2and HNO
3deng.In this experiment, the mist of the NO of 1ppm and air (volumetric mixture ratio is 1 ︰ 1) is continuously passed in the shading closed reactor that photochemical catalyst is housed, the in the situation that of illumination, NO is oxidized, by measuring the NO concentration the gas flowing out from reactor, NO concentration before and after contrast illumination obtains its resolution ratio, thereby realizes the evaluation of the catalytic activity of this photochemical catalyst.The concentration of NO gas adopts Yanaco ELC-88A type NO
xanalysis-e/or determining, light source is used high-pressure sodium lamp.Use simultaneously and there is the commercial powder of highly active titanium dioxide (P-25, German Degussa company produce) as with reference to sample.Concrete characterizing method is as follows: powder sample is filled in the middle of the sample cell that an area is 20 * 15 * 0.5mm, and being fixed to a volume is 373 cm
3closed reactor in.Respectively the dry air of the NO Standard Gases of 100mL and 100mL is passed in the glass gas cylinder that volume is 200mL, by being mixed to get fully the NO/Air mist (NO concentration is 1ppm) of 200mL.In the situation that there is no illumination, (dark condition) do not pass into the NO gas uniform speed of above-mentioned 1ppm in reactor, and makes it reach stable state.The high-pressure sodium lamp of 450W of usining irradiates sample as light source, the evaluation to the photocatalytic activity of NO gas.As can be seen from Figure 9, than commercial P25 and doped graphene photocatalysis material of titanium dioxide not, boron doped graphene/Rutile Type TiO that embodiment 1 makes
2nanometer rods composite photocatalyst material has the strongest nitrogen oxide degradation capability.
embodiment 2
Adopt document ACS Nano. 2010,4 (8): the disclosed method of 4806-4814 is prepared graphene oxide, take 40mg graphene oxide, add 20mL deionized water, ultrasonic dispersion 0.75 hour, obtain graphene oxide dispersion liquid, add subsequently the titanium trichloride solution that 0.61g sodium borohydride and 3.38mL mass percent concentration are 20%, on magnetic stirring apparatus, stir 40min, ultrasonic agitation 30min again, finally solution is proceeded in 50mL water heating kettle, at 160 ℃ of temperature, hydro-thermal reaction is 16 hours, the sediment obtaining is used after deionized water and ethanol difference centrifuge washing successively, at 50 ℃ of temperature, vacuum drying is 12 hours, with agate mortar, grind to form uniform powder again, obtain boron doped graphene/Rutile Type TiO
2nanometer rods composite photocatalyst material.
embodiment 3
Adopt document ACS Nano. 2010,4 (8): the disclosed method of 4806-4814 is prepared graphene oxide, take 8mg graphene oxide, add 15mL deionized water, ultrasonic dispersion 0.5 hour, obtain graphene oxide dispersion liquid, add subsequently the titanium trichloride solution that 0.9g sodium borohydride and 13.52mL mass percent concentration are 20%, on magnetic stirring apparatus, stir 50min, ultrasonic agitation 50min again, finally solution is proceeded in 50mL water heating kettle, at 200 ℃ of temperature, hydro-thermal reaction is 12 hours, the sediment obtaining is used after deionized water and ethanol difference centrifuge washing successively, at 70 ℃ of temperature, vacuum drying is 8 hours, with agate mortar, grind to form uniform powder again, obtain boron doped graphene/Rutile Type TiO
2nanometer rods composite photocatalyst material.
Claims (4)
1. a boron doped graphene/TiO
2the preparation method of nanometer rods catalysis material, take graphene oxide, sodium borohydride, titanium trichloride is 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 the < < of the American Chemical Society nanometer > > periodical disclosed method of the 4th volume 4806-4814 page in 2010 to prepare graphene oxide;
Step 2: take 8～80mg graphene oxide, add 15～25ml deionized water, ultrasonic dispersion, obtains graphene oxide dispersion liquid;
Step 3: add sodium borohydride and titanium trichloride solution in graphene oxide dispersion liquid, carry out hydro-thermal reaction after stirring, obtain 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 3, adds the titanium trichloride solution that 0.3～0.9g sodium borohydride and 3.38～13.52mL mass percent concentration are 20% in graphene oxide dispersion liquid.
3. boron doped graphene/TiO according to claim 1
2the preparation method of nanometer rods catalysis material, is characterized in that, in described step 3, and at the temperature of 160～200 ℃, hydro-thermal reaction 12～16 hours.
4. 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, at the temperature of 50～70 ℃, vacuum drying is 8～12 hours.
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| CN111905807A (en) * | 2020-07-06 | 2020-11-10 | 安徽理工大学 | High instantaneous photocurrent nanometer TiO2Polyaniline/graphene composite material and preparation method thereof |
| CN111944267A (en) * | 2020-07-30 | 2020-11-17 | 山东大学 | Preparation method of boron-doped graphene composite material and application of boron-doped graphene composite material as negative dielectric material |
| CN111944267B (en) * | 2020-07-30 | 2021-06-29 | 山东大学 | Preparation method of boron-doped graphene composite material and application of boron-doped graphene composite material as negative dielectric material |
| CN114643050A (en) * | 2022-05-19 | 2022-06-21 | 浙江晟格生物科技有限公司 | Composite catalyst for improving lactose isomerization yield, preparation method and application |
| 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 |
| CN115072842A (en) * | 2022-06-17 | 2022-09-20 | 深圳大学 | Composite electrode, preparation method thereof and plasma disinfectant water generating device |
| CN115072842B (en) * | 2022-06-17 | 2023-10-27 | 深圳市荔辉医疗科技有限公司 | Composite electrode, preparation method thereof and plasma sterilizing water generating device |
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