CN104624220B - One prepares TiO2the method of/rGO composite - Google Patents
One prepares TiO2the method of/rGO composite Download PDFInfo
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- CN104624220B CN104624220B CN201510069023.2A CN201510069023A CN104624220B CN 104624220 B CN104624220 B CN 104624220B CN 201510069023 A CN201510069023 A CN 201510069023A CN 104624220 B CN104624220 B CN 104624220B
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- 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
- Y02E60/50—Fuel cells
Abstract
The present invention relates to one and prepare TiO2The method of/rGO composite, belongs to electrocatalysis material preparing technical field.The method of the present invention, including butyl titanate, graphene oxide, absolute ethyl alcohol, ethylene glycol, urea and ammonium fluoride, the constant temperature step of 8 12 hours under the conditions of pH=1 4, T=190 230 DEG C.TiO prepared by the method for the present invention2/ rGO composite, particle diameter between 3 5nm, the evengranular surface being attached to redox graphene of modified nano-titanium dioxide.Compared with graphene oxide, in the material with carbon element of redox graphene, oxydant substantially reduces；N and F element has been doped to nano-TiO2Lattice in formed modified Nano TiO2, and doping is controlled.Raw material is cheap and easy to get, and preparation manipulation is simple, and last handling process is simple, and response parameter is easily controllable, and flow process is short, and energy consumption is low, and products obtained therefrom electrocatalysis characteristic is good.
Description
Technical field
The present invention relates to one and prepare TiO2The method of/rGO composite, belongs to electrocatalysis material preparing technical field.
Background technology
Fuel cell be a kind of chemical energy that will be present in chemical fuel and oxidant directly, continuous print be converted into electric energy
TRT, because it has cleaning, efficiently and do not rely on the features such as any other energy, and more and more closed
Note.For alkaline fuel cell, the hydrogen reduction performance of cathode material is the key technology of its development of restriction.Electricity on the whole
Chemical oxygen reduction reaction is because electrode material, surface nature and pH value of solution are worth difference, and reaction mechanism is the most different, generally can be divided into
Two electron reactions, direct four electron reactions and two step two electronics (2+2) courses of reaction, because four electron reaction processes can obtain
It is construed to preferable hydrogen reduction approach to more electric energy.
Generally, the Pt/C catalyst load of Pt simple substance prepared on the carbon material is the most frequently used electrocatalysis material, is used as
The material with carbon element of carrier typically has ordinary carbon black, Vulan XC-72 carbon black, CNT and multiple-wall carbon nanotube etc..But due to
Material with carbon element is easily corroded, and causes adhering to superincumbent noble metal and comes off from electrode surface or be agglomerated into bulky grain, thus makes
Become catalysis material catalytic performance and the decline of stability.Therefore it is highly desirable to find under fuel cell operating condition, performance
Stable non-carbon support replaces carbon support material conventional in catalyst, to improve the durability of fuel cell.
Transition metal oxide, such as TiO2、SnO2、WO3And CeO2Deng, because having good chemical stability, anticorrosive
Property, and and carried metal between strong interaction and paid close attention to widely.Especially TiO2It is considered to be a kind of energy generation
Excellent carrier for material with carbon element.As the carrier of metal, TiO in electrocatalysis material2Can be by strong between metal and carrier
Interaction and improve the catalytic performance of material.Platinum grain is born by Sangaraju Shanmugam et al. with sonochemical method
It is downloaded to porous nano TiO2Going up and have studied the oxygen reduction activity of this catalysis material, result shows, Pt/TiO2C is loaded to than Pt
Electrocatalytic oxidation reducing activity on material is strong.Sheng-Yang Huang et al. is under study for action it has also been found that TiO2And it is strong between Pt
Interaction can improve the hydrogen reduction performance of this material.Although the catalysis material of researcher's hydrogen reduction in the basic conditions
Aspect has done substantial amounts of research, but up to the present, TiO2It is only used as the carrier of electrocatalysis material, is not used as
Electrocatalysis material.Mingyan Wang et al. reports a kind of by Co3O4Nanometer rods loads to redox graphene (rGO) sheet
Short-cut method on layer, obtained Co3O4/ rGO composite shows very in the electrocatalytic oxidation reduction test of alkaline solution
Good electrocatalysis characteristic.But there is presently no about by modification TiO2Directly load on redox graphene lamella, system
The report of the synthetic method of standby one-tenth high-performance electric catalytic oxidation-reduction material.
Summary of the invention
It is an object of the invention to, it is provided that a kind of by modified Nano TiO2Directly load to redox graphene lamella
On, prepare TiO2The method of/rGO composite；The method uses hydro-thermal one kettle way, and technique is simple；Prepared TiO2/ rGO is multiple
Condensation material possesses efficient electric catalytic oxidation-reduction performance in the basic conditions.
Technical scheme
One prepares TiO2The method of/rGO composite, including butyl titanate, graphene oxide, absolute ethyl alcohol, second
Glycol, urea and ammonium fluoride, the constant temperature step of 8-12 hour under the conditions of pH=1-4, T=190-230 DEG C.
Product absolute ethanol washing after being terminated by above-mentioned constant temperature, then washs with redistilled water, then distillation of reducing pressure；
Obtain powder TiO of black2/ rGO composite.
TiO prepared by the method for the present invention2/ rGO composite, through SEM Yu TEM characterize, particle diameter 3-5nm it
Between, the evengranular surface being attached to redox graphene of modified nano-titanium dioxide.XPS shows, the method for the present invention
The TiO of preparation2Containing following several elements in/rGO composite: N, F, O, Ti, C；Compared with graphene oxide, reduction-oxidation
In the material with carbon element of Graphene, oxydant substantially reduces；N and F element has been doped to nano-TiO2Lattice in formed modification receive
Rice TiO2, and doping is controlled.As can be seen here, the method for the present invention, with butyl titanate and graphene oxide as raw material, with
Absolute ethyl alcohol is organic solvent, with ethylene glycol as dispersant with reducing agent, with urea and ammonium fluoride as modifying agent；Little at constant temperature 10
Complete following three process: 1.N element and F element are successfully doped to nano-TiO time during simultaneously2Lattice in shape
Become the Anatase modified Nano TiO of N, F codope2Particle；2. graphene oxide GO is reduced to redox graphene
rGO；3. make modified Nano TiO2It is uniformly adhered to the surface of redox graphene lamella, is formed and possess efficient electrocatalytic oxidation
The TiO of reducing property2/ rGO composite.That is, the present invention is a kind of next step charging, method of one pot reaction of liquid-phase system；
Operation is simple for the method, and last handling process is simple, and response parameter is easily controllable, flow process section, and energy consumption is low, and raw material is inexpensive easily
?.
It addition, cyclic voltammetry (CV) result shows, TiO prepared by the preparation method of the present invention2/ rGO composite exists
In the 0.1 M KOH solution that oxygen is saturated, having high electrocatalytic oxidation reducing property, initial oxidation current potential is at about-0.2 V,
Big hydrogen reduction electric current can reach 10-5 mA cm-2The order of magnitude.Show through chronoamperometry test, through 16, the electricity of 000 s
After test chemical, TiO2When the current density of/rGO composite is the most up to start about 90%, has extraordinary stable
Property, and about 74% when commercially available Pt/C only starts under same experimental conditions.Rotating disk electrode (r.d.e) (RDE) and Rotation ring disk electrode electricity
The test of pole (RRDE) shows TiO2The oxygen reduction reaction carried out on/rGO composite is four electron reactions that selectivity is the highest
System (as the catalyst of four electronics electrochemical oxygen reduction reactions).So, the method for the present invention is also equipped with products obtained therefrom electricity and urges
Change hydrogen reduction performance is good, good stability, the highest advantage.
Said method, it is preferred that use following concrete operation step to complete:
Butyl titanate, absolute ethyl alcohol, ethylene glycol add in reactor, and stirring is to forming faint yellow settled solution, then adds
Entering urea, ammonium fluoride and graphene oxide, with the salt acid for adjusting pH of 6mol/L, stir after clarifying to solution in 200 DEG C, constant temperature is anti-
It is cooled to room temperature after answering 10 hours；With redistilled water, product is washed twice again after product absolute ethanol washing more than twice
Above, then decompression distill.The advantage using this addition step is: 1. prevent and treat tetrabutyl titanate hydrolysis；2. walk than other
Suddenly the more time is saved.
Said method, it is preferred that graphene oxide is 1.5-4.5:100 with the mol ratio of butyl titanate.Now, made
Standby TiO2/ rGO composite, the content of redox graphene is 1.5-4.5%；Possesses efficient electric catalytic oxidation-reduction
Energy.The content of described redox graphene: refer to the TiO possessing efficient electric catalytic oxidation-reduction performance2In/rGO composite
The molar content of redox graphene.
Said method, it is preferred that urea, ammonium fluoride are 1:100(urea and metatitanic acid four with the mol ratio of butyl titanate
The mol ratio of butyl ester is 1:100, and ammonium fluoride is 1:100 with the mol ratio of butyl titanate)；Now, prepared TiO2/rGO
In composite, the doping relative to modified nano-titanium dioxide of N, F respectively 1.07-1.19%, 0.95-1.04%(rub
That content)；The doping being somebody's turn to do can make the electrocatalytic oxidation reducing property of modified nano-titanium dioxide reach more excellent.
Said method, it is preferred that the volume ratio of butyl titanate, absolute ethyl alcohol and ethylene glycol is 10:10:3.Use this body
The advantage of long-pending ratio is: on the basis of guaranteeing to generate required electrocatalysis material, can save raw material to greatest extent, reduces anti-
Answer cost.
In order to preferably possessed the TiO of efficient electric catalytic oxidation-reduction performance2/ rGO composite, it should however be noted that
In addition to the moisture in the hydrochloric acid of acidity regulator 6mol/L, system does not add other moisture；Solvent uses anhydrous second
Alcohol, to ensure TiO in the electrocatalysis material obtained2Particle uniformly and be pure Anatase；Use ethylene glycol as also
Former dose to ensure that graphene oxide is reduced.
Beneficial effect
Raw material is cheap and easy to get, and preparation manipulation is simple, and last handling process is simple, and response parameter is easily controllable, and flow process is short,
Energy consumption is low, and products obtained therefrom electrocatalysis characteristic is good.
Accompanying drawing explanation
Fig. 1 is ESEM (SEM) collection of illustrative plates of 4 kinds of samples, and wherein figure a is TiO2, figure b is TiO2/ (1.5%) rGO, schemes c
For TiO2/ (3.0%) rGO, figure d are TiO2/(4.5%)rGO。
Fig. 2 is transmission electron microscope (TEM) collection of illustrative plates of 4 kinds of samples, and wherein figure a is TiO2, figure b is TiO2/ (1.5%) rGO, schemes c
For TiO2/ (3.0%) rGO, figure d are TiO2/(4.5%)rGO。
Fig. 3 is 4 kinds of sample specific surface area test (BET) collection of illustrative plates；
Fig. 4 is Raman (RM) collection of illustrative plates of 3 samples；
Fig. 5 is 4 sample X-ray electron spectrum (XPS) collection of illustrative plates；Wherein, figure a is that the XPS of 4 kinds of samples composes that (each element is shown in entirely
Figure a marks above dotted line) and four kinds of samples in each element containing scale, figure b is TiO2The high score of C 1s in/(1.5%) rGO
Distinguish that XPS collection of illustrative plates, figure c are TiO2The high-resolution XPS collection of illustrative plates of C 1s in/(3.0%) rGO, figure d is TiO2C 1s in/(4.5%) rGO
High-resolution XPS collection of illustrative plates, figure e is TiO2The high-resolution XPS collection of illustrative plates of N 1s in/rGO, figure f is TiO2The high-resolution of F 1s in/rGO
XPS collection of illustrative plates；
Cyclic voltammetry curve (CV) figure that Fig. 6 is four kinds of samples in the saturated 0.1 M KOH solution of oxygen and nitrogen,
Illustration a is TiO2, figure b is TiO2/ (1.5%) rGO, figure c are TiO2/ (3.0%) rGO, figure d are TiO2/(4.5%)rGO；
Fig. 7 is the Tafel collection of illustrative plates of 3 kinds of samples；
Fig. 8 be 3 kinds of samples and commercially available Pt/C material respective time m-electric current (i-t) curve；Wherein 3 kinds of samples time
M-electric current (i-t) curve almost overlaps；
The rotating disk electrode (r.d.e) (RED) that Fig. 9 is the lower 3 kinds of samples of room temperature in the saturated 0.1 M KOH solution of oxygen is bent
Line chart, illustration is the Koutechy-Levich curve map under different electricity electromotive force and calculated electro transfer number；Wherein its
Middle figure a is TiO2/ (1.5%) rGO, figure b are TiO2/ (3.0%) rGO, figure c are TiO2/(4.5%)rGO；
The rotating ring disk electrode (r.r.d.e) that Figure 10 figure a is the lower 3 kinds of samples of room temperature in the saturated 0.1 M KOH solution of oxygen
(RRED) curve map, figure b is that 3 kinds of samples generate H in electrochemistry experiment2O2Percentage composition, illustration is the electronics of 3 kinds of samples
Transfer number；
Marked TiO in Fig. 1-102For modified Nano TiO prepared in comparative example 12；
Figure 11 is that the hydro-thermal one pot process present invention possesses efficient electric catalytic oxidation-reduction performance TiO2/ rGO composite
Preparation technology schematic diagram.
Detailed description of the invention
Embodiment 1
In the small beaker of 50mL, while magnetic stirrer, add 10.00mL absolute ethyl alcohol, 3.00mL ethylene glycol
Stoste (pure ethylene glycol), is slowly added to raw material butyl titanate 10.00mL, stirs 5 min, forms light yellow transparent liquid, adds
Enter ammonium fluoride 0.867 gram, 1.406 grams of urea, graphene oxide 2mL (1g/100mL), stir to solution clarification (about 5 min),
Finally it is added dropwise over hydrochloric acid 16.00 mL of 6mol/L, after being sufficiently stirred for, reaction solution is proceeded to the autoclave of 100mL
In, it being heated to 200 DEG C, constant temperature took out after 10 hours, and product is with absolute ethanol washing three times, then washs three with redistilled water
Secondary, put into distillation 20 minutes of reducing pressure at 50 DEG C in vacuum distillation apparatus, obtain the pulverulent solids of black, be and possess efficient electric
The TiO of catalytic oxidation-reduction performance2/ rGO composite TiO2/(1.5%)rGO。
Characterizing through SEM Yu TEM, the evengranular surface being attached to rGO of modified nano-titanium dioxide, particle diameter is 4 ± 2
nm.BET outcome research proves, the specific surface area of material is 207.8 m2/g.Raman (RM) spectrum test shows, graphene oxide
(GO) being reduced to redox graphene (rGO) during Hydrothermal Synthesis, D peak is I with the ratio at G peakD/IG=1.29。XPS
Showing, containing N, F, O, Ti, C in composite, wherein the content of N Yu F element is all at about 1.0 %, and the content of rGO is 1.5
About %, compared with graphene oxide, in the material with carbon element of redox graphene, oxydant substantially reduces, and proves material further
Graphene oxide in material is reduced to redox graphene.Cyclic voltammetry (CV) result shows, composite is at oxygen
In 0.1 saturated M KOH solution, having high electrocatalytic oxidation reducing property, initial oxidation current potential is at about-0.2 V, according to material
The Tafel curve of material records maximum oxygen reduction current and can reach 3.35 × 10-6 mA cm-2.Chronoamperometry (i-t) experiment knot
Fruit shows, through 16, after the electro-chemical test of 000 s after, about 91 % when current density of this material is initial.Rotational circle
The test result of disc electrode (RDE) and rotating ring disk electrode (r.r.d.e) (RRDE) shows that this material is that selectivity is the highest to the reaction of hydrogen reduction
Four electron reaction systems.
Embodiment 2
In the small beaker of 50mL, while magnetic stirrer, add 10.00mL absolute ethyl alcohol, 3.00mL ethylene glycol
Stoste, is slowly added to raw material butyl titanate 10.00mL, stirs 5min, forms light yellow transparent liquid, adds ammonium fluoride
0.867 gram, 1.406 grams of urea, graphene oxide 4mL (1g/100mL), stirs to solution clarification (about 5 min), the most dropwise
Add hydrochloric acid 16.00 mL of 6mol/L, after being sufficiently stirred for, reaction solution is proceeded in the autoclave of 100 mL, heating
To 200 DEG C, constant temperature took out after 10 hours, and product is with absolute ethanol washing three times, then washs three times with redistilled water, puts into and subtracts
In pressure distilling apparatus, decompression distillation 20 minutes at 50 DEG C, obtain the pulverulent solids of black, are and possess efficient electrocatalytic oxidation also
The TiO of originality energy2/ rGO composite TiO2/(3.0%)rGO。
Characterizing through SEM Yu TEM, the evengranular surface being attached to rGO of modified nano-titanium dioxide, particle diameter is 2 ± 2
nm.BET outcome research proves, the specific surface area of material is 316.2 m2/g.Raman (RM) spectrum test shows, graphene oxide
(GO) being reduced to redox graphene (rGO) during Hydrothermal Synthesis, D peak is I with the ratio at G peakD/IG=1.35。XPS
Showing, containing N, F, O, Ti, C in composite, wherein the content of N Yu F element is all at about 1.0 %, and the content of rGO is 3.0
About %, compared with graphene oxide, in the material with carbon element of redox graphene, oxydant substantially reduces, and proves material further
Graphene oxide in material is reduced to redox graphene.Cyclic voltammetry (CV) result shows, composite is at oxygen
In 0.1 saturated M KOH solution, having high electrocatalytic oxidation reducing property, initial oxidation current potential is at about-0.2 V, according to material
The Tafel curve of material records maximum oxygen reduction current and can reach 1.29 × 10-5 mA cm-2.Chronoamperometry (i-t) shows, warp
Cross 16, about 92 % after the electrochemistry experiment of 000 s, when the current density of this material is initial.Rotating disk electrode (r.d.e)
And the test of rotating ring disk electrode (r.r.d.e) (RRDE) shows that hydrogen reduction is reacted for the highest four electron back of selectivity by this material (RDE)
Answer system.
Embodiment 3
In the small beaker of 50mL, while magnetic stirrer, add 10.00mL absolute ethyl alcohol, 3.00mL ethylene glycol
Stoste, is slowly added to raw material butyl titanate 10.00mL, stirs 5min, forms light yellow transparent liquid, adds ammonium fluoride
0.867 gram, 1.406 grams of urea, graphene oxide 6mL (1g/100mL) is sufficiently stirred for solution to clarifying (about 5 min), finally
It is added dropwise over the hydrochloric acid 16.00mL of 6mol/L, after being sufficiently stirred for, proceeds to reaction solution, in the autoclave of 100ml, add
Heat is to 200 DEG C, and constant temperature took out after 10 hours, and product is with absolute ethanol washing three times, then with redistilled water washing three times, puts into
In vacuum distillation apparatus, decompression distillation 20 minutes at 50 DEG C, obtain the pulverulent solids of black, are and possess efficient electrocatalytic oxidation
The TiO of reducing property2/ rGO composite TiO2/(4.5%)rGO。
Characterizing through SEM Yu TEM, the evengranular surface being attached to rGO of modified nano-titanium dioxide, particle diameter is 3 ± 2
nm.BET outcome research proves, the specific surface area of material is 382.2 m2/g.Raman (RM) spectrum test shows, graphene oxide
(GO) being reduced to redox graphene (rGO) during Hydrothermal Synthesis, D peak is I with the ratio at G peakD/IG=1.31。XPS
Showing, containing N, F, O, Ti, C in composite, wherein the content of N Yu F element is all at about 1.0 %, and the content of rGO is 4.5
About %, compared with graphene oxide, in the material with carbon element of redox graphene, oxydant substantially reduces, and proves material further
Graphene oxide in material is reduced to redox graphene.Cyclic voltammetry (CV) result shows, composite is at oxygen
In 0.1 saturated M KOH solution, having high electrocatalytic oxidation reducing property, initial oxidation current potential is at about-0.2 V, according to material
The Tafel curve of material records maximum oxygen reduction current and can reach 5.74 × 10-6 mA cm-2.Chronoamperometry (i-t) shows, warp
Cross 16, about 90 % after the electrochemistry experiment of 000 s, when the current density of this material is initial.Rotating disk electrode (r.d.e)
And the test of rotating ring disk electrode (r.r.d.e) (RRDE) shows that hydrogen reduction is reacted for the highest four electron back of selectivity by this material (RDE)
Answer system.
Comparative example 1
In the small beaker of 50mL, while magnetic stirrer, add 10.00mL absolute ethyl alcohol, 3.00mL ethylene glycol
Stoste, is slowly added to raw material butyl titanate 10.00mL, stirs 10min, forms light yellow transparent liquid, adds ammonium fluoride
0.867 gram, 1.406 grams of urea, stirring is completely dissolved to solid particle, is finally added dropwise over the hydrochloric acid 16.00ml of 6mol/L,
Stirring after clarifying to solution, proceeded to by reaction solution in the autoclave of 100mL, be heated to 200 DEG C, constant temperature took after 10 hours
Going out, product is with absolute ethanol washing three times, then washs three times with redistilled water, puts in vacuum distillation apparatus and reduces pressure at 50 DEG C
Distill 20 minutes, obtain flaxen pulverulent solids, be N element and F element is successfully doped to nano-TiO2Lattice
The Anatase modified Nano TiO of N, F codope2Particle.
Characterizing through SEM Yu TEM, modified nano-titanium dioxide particle, particle diameter is 5 ± 2 nm.BET outcome research proves,
The specific surface area of material is 124.6 m2/g.XPS shows, containing N, F, O, Ti, C in composite, and wherein the containing of N with F element
Amount is all about 1%, and C element derives from the carbon in instrument test and pollutes.Cyclic voltammetry (CV) result shows, this material is at oxygen
In the 0.1 M KOH solution that gas is saturated, there is no any electrocatalytic oxidation reducing property.
In the electrocatalytic oxidation reduction test of above-described embodiment and comparative example, reference electrode used is saturated calomel electrode, to electricity
Extremely platinum electrode, electrolyte is 0.1 M KOH solution, and if no special instructions, the sweep speed in electrochemical test is all 5
mV/s。
Claims (5)
1. prepare TiO for one kind2The method of/rGO composite, adds reactor including butyl titanate, absolute ethyl alcohol, ethylene glycol
In, stirring, to forming faint yellow settled solution, adds urea, ammonium fluoride and graphene oxide, at pH=1-4, T=190-230
The constant temperature step of 8-12 hour under the conditions of DEG C.
Method the most according to claim 1, it is characterised in that
Butyl titanate, absolute ethyl alcohol, ethylene glycol add in reactor, and stirring, to forming faint yellow settled solution, adds urine
Element, ammonium fluoride and graphene oxide, with the salt acid for adjusting pH of 6mol/L, stir after clarifying to solution in 200 DEG C, isothermal reaction
It is cooled to room temperature after 10 hours；After product absolute ethanol washing more than twice again with redistilled water product washed twice with
On, then decompression distill.
Method the most according to claim 1 and 2, it is characterised in that graphene oxide with the mol ratio of butyl titanate is
1.5-4.5:100.
Method the most according to claim 1 and 2, it is characterised in that urea, ammonium fluoride are equal with the mol ratio of butyl titanate
For 1:100.
Method the most according to claim 1 and 2, it is characterised in that the volume of butyl titanate, absolute ethyl alcohol and ethylene glycol
Ratio is 10:10:3.
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| CN106654304A (en) * | 2016-10-14 | 2017-05-10 | 济南大学 | CuO/rGO composite material having efficient electrocatalysis oxygen reducing performance |
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| CN111244406A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Fluorinated graphene modified titanium dioxide material, and preparation and application thereof |
| CN109713324B (en) * | 2018-12-21 | 2021-06-11 | 陕西师范大学 | Ti4O7/Ti3O5Mixed-phase fiber electrocatalyst and application thereof in oxygen reduction |
| CN109718752B (en) * | 2019-01-27 | 2021-11-12 | 安徽大学 | graphene/TiO2Nanocomposite and method for preparing same |
| CN113130884B (en) * | 2021-04-07 | 2024-02-13 | 福建大成新能源科技有限公司 | F-doped TiO 2 Preparation method and application of-B |
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| CN102380364A (en) * | 2011-09-02 | 2012-03-21 | 武汉大学 | Preparation method of TiO2/graphene composite film |
| CN103207222A (en) * | 2013-04-12 | 2013-07-17 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene nano-material electrochemical sensor by atomic layer deposition process |
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