CN104624220A - Preparation method of TiO2/rGO composite - Google Patents
Preparation method of TiO2/rGO composite Download PDFInfo
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- CN104624220A CN104624220A CN201510069023.2A CN201510069023A CN104624220A CN 104624220 A CN104624220 A CN 104624220A CN 201510069023 A CN201510069023 A CN 201510069023A CN 104624220 A CN104624220 A CN 104624220A
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- tio
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- tio2
- butyl titanate
- graphene oxide
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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 invention relates to a preparation method of a TiO2/rGO composite, and belongs to the technical field of electro-catalytic material preparation. The method comprises the step of keeping butyl titanate, oxidized graphene, absolute ethyl alcohol, glycol, urea and ammonium fluoride at a constant temperature being 190-230 DEG C for 8-12h under the condition of pH value being 1-4. The particle size of the TiO2/rGO composite prepared by adopting the method is 3-5nm, and modified nano-TiO2 particles are uniformly attached to the surface of reduction-oxidation graphene. Compared with oxidized graphene, an oxygen-containing component of a carbon material in the reduction-oxidation graphene is reduced significantly; and N and F elements are doped in lattices of nano-TiO2 to form modified nano-TiO2, and the doping quantity is controllable. Raw materials are cheap and easy to obtain; the preparation operation is simple and easy; the aftertreatment process is simple; reaction parameters are easy to control; the flow is short; the energy consumption is low; and the electro-catalytic performance of the obtained composite is good.
Description
Technical field
the present invention relates to one and prepare TiO
2the method of/rGO composite, belongs to electrocatalysis material preparing technical field.
Background technology
Fuel cell is a kind of by the TRT that the chemical energy be present in chemical fuel and oxidant is direct, continuous print is converted into electric energy, has clean, efficient and does not rely on the features such as any other energy, and receive increasing concern because of it.For alkaline fuel cell, the hydrogen reduction performance of cathode material is the key technology of its development of restriction.Electrochemical oxygen reduction reaction is because electrode material, surface nature and pH value of solution are worth different on the whole, reaction mechanism is also different, four electron reaction processes generally can be divided into two electron reactions, direct four electron reactions and two step two electronics (2+2) courses of reaction, because can obtain more electric energy and be construed to desirable hydrogen reduction approach.
Usually, be the most frequently used electrocatalysis material by the Pt/C catalyst that the load of Pt simple substance is prepared on the carbon material, the material with carbon element as carrier generally has ordinary carbon black, Vulan XC-72 carbon black, CNT and multiple-wall carbon nanotube etc.But because material with carbon element is easily corroded, cause adhering to superincumbent noble metal and come off from electrode surface or be agglomerated into bulky grain, thus cause the decline of catalytic material catalyzes performance and stability.Therefore be necessary very much to find under fuel cell operating condition, the non-carbon support of stable performance replaces carbon support material conventional in catalyst, to improve the durability of fuel cell.
Transition metal oxide, as TiO
2, SnO
2, WO
3and CeO
2deng because have good chemical stability, corrosion resistance, and and carried metal between strong interaction and being paid close attention to widely.Especially TiO
2, be considered to a kind of excellent carrier that can replace material with carbon element.As the carrier of metal in electrocatalysis material, TiO
2the catalytic performance of material can be improved by interaction strong between metal and carrier.Platinum grain is loaded to porous nano TiO with sonochemical method by the people such as Sangaraju Shanmugam
2go up and have studied the oxygen reduction activity of this catalysis material, result shows, Pt/TiO
2the electrocatalytic oxidation reducing activity loaded on C material than Pt is strong.The people such as Sheng-Yang Huang also find TiO under study for action
2and interaction strong between Pt can improve the hydrogen reduction performance of this material.Although large quantifier elimination has been done in the catalysis material aspect of researcher's hydrogen reduction in the basic conditions, up to the present, TiO
2just be used as the carrier of electrocatalysis material, be not used as electrocatalysis material.The people such as Mingyan Wang report a kind of by Co
3o
4nanometer rods loads to the short-cut method on redox graphene (rGO) lamella, the Co obtained
3o
4/ rGO composite shows good electrocatalysis characteristic in the electrocatalytic oxidation reduction test of alkaline solution.But at present also not about by modification TiO
2directly load on redox graphene lamella, be prepared into the report of the synthetic method of high-performance electric catalytic oxidation-reduction material.
Summary of the invention
The object of the invention is to, provide a kind of by modified Nano TiO
2directly load on redox graphene lamella, preparation TiO
2the method of/rGO composite; The method adopts hydro-thermal one kettle way, and technique is simple; Prepared TiO
2/ rGO composite possesses efficient electric catalytic oxidation-reduction performance in the basic conditions.
Technical scheme
One prepares TiO
2the method of/rGO composite, comprises butyl titanate, graphene oxide, absolute ethyl alcohol, ethylene glycol, urea and ammonium fluoride, the step of constant temperature 8-12 hour under pH=1-4, T=190-230 DEG C of condition.
Product absolute ethanol washing after above-mentioned constant temperature is terminated, then with second distillation water washing, then decompression distillation; Obtain the Powdered TiO of black
2/ rGO composite.
TiO prepared by method of the present invention
2/ rGO composite, through SEM and TEM characterize, particle diameter between 3-5nm, the evengranular surface being attached to redox graphene of modified nano-titanium dioxide.XPS shows, TiO prepared by method of the present invention
2containing following several element in/rGO composite: N, F, O, Ti, C; Compared with graphene oxide, in the material with carbon element of redox graphene, oxydant significantly reduces; N and F element is doped to nano-TiO
2lattice in form modified Nano TiO
2, and doping is controlled.As can be seen here, method of the present invention, with butyl titanate and graphene oxide for raw material, being organic solvent with absolute ethyl alcohol, take ethylene glycol as dispersant and reducing agent, with urea and ammonium fluoride for modifier; Complete following three processes: 1.N element and F element are successfully doped to nano-TiO in the constant temperature process of 10 hours simultaneously
2lattice in form the Anatase modified Nano TiO of N, F codope
2particle; 2. graphene oxide GO is reduced to redox graphene rGO; 3. make modified Nano TiO
2be attached to the surface of redox graphene lamella uniformly, form the TiO possessing efficient electric catalytic oxidation-reduction performance
2/ rGO composite.That is, the present invention is a kind of next step method that is reinforced, one pot reaction of liquid-phase system; Operation is simple for the method, and last handling process is simple, and response parameter is easy to control, and flow process section, energy consumption is low, and raw material is cheap and easy to get.
In addition, cyclic voltammetry (CV) result shows, TiO prepared by preparation method of the present invention
2/ rGO composite is in the saturated 0.1 M KOH solution of oxygen, and have high electrocatalytic oxidation reducing property, initial oxidation current potential is at about-0.2 V, and maximum oxygen reduction current can reach 10
-5mA cm
-2the order of magnitude.Show through chronoamperometry test, through 16, after the electro-chemical test of 000 s, TiO
2the current density of/rGO composite is still up to about 90% when starting, and has extraordinary stability, and about 74% when commercially available Pt/C is only beginning under same experimental conditions.The test of rotating disk electrode (r.d.e) (RDE) and rotating ring disk electrode (r.r.d.e) (RRDE) shows TiO
2the oxygen reduction reaction that/rGO composite carries out is selective four very high electron reaction systems (catalyst as four electronics electrochemical oxygen reduction reactions).So method of the present invention also possesses that products obtained therefrom electrocatalytic oxidation reducing property is good, good stability, selective high advantage.
Said method, preferably, adopts following concrete operation step to complete:
Butyl titanate, absolute ethyl alcohol, ethylene glycol add in reactor, be stirred to and form faint yellow settled solution, then add urea, ammonium fluoride and graphene oxide, with the salt acid for adjusting pH of 6mol/L, be stirred to solution clarification after in 200 DEG C, isothermal reaction was cooled to room temperature after 10 hours; Product is washed twice above with redistilled water again after product absolute ethanol washing more than twice, then decompression distillation.The advantage of this addition step is adopted to be: 1. prevent and treat tetrabutyl titanate hydrolysis; 2. save the more time than other steps.
Said method, preferably, the mol ratio of graphene oxide and butyl titanate is 1.5-4.5:100.Now, prepared TiO
2/ rGO composite, the content of redox graphene is 1.5-4.5%; Possesses efficient electric catalytic oxidation-reduction performance.The content of described redox graphene: refer to the TiO possessing efficient electric catalytic oxidation-reduction performance
2the molar content of redox graphene in/rGO composite.
Said method, preferably, the mol ratio that the mol ratio of urea, ammonium fluoride and butyl titanate is 1:100(urea and butyl titanate is 1:100, and the mol ratio of ammonium fluoride and butyl titanate is 1:100); Now, prepared TiO
2in/rGO composite, N, F are respectively 1.07-1.19%, 0.95-1.04%(molar content relative to the doping of modified nano-titanium dioxide); The doping of being somebody's turn to do can make the electrocatalytic oxidation reducing property of modified nano-titanium dioxide reach more excellent.
Said method, preferably, the volume ratio of butyl titanate, absolute ethyl alcohol and ethylene glycol is 10:10:3.Adopting the advantage of this volume ratio to be: guaranteeing to generate on the basis of required electrocatalysis material, raw material can be saved to greatest extent, reducing reaction cost.
In order to the TiO of efficient electric catalytic oxidation-reduction performance can be possessed preferably
2/ rGO composite, should note: except the moisture in the hydrochloric acid of acidity regulator 6mol/L, no longer add other moisture in system; Solvent adopts absolute ethyl alcohol, to ensure TiO in the electrocatalysis material that obtains
2uniform particles and be pure Anatase; Adopt ethylene glycol as reducing agent 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 easy to control, and flow process is short, and 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 scheming a is TiO
2, figure b is TiO
2/ (1.5%) rGO, figure c is TiO
2/ (3.0%) rGO, figure d is TiO
2/ (4.5%) rGO.
Fig. 2 is transmission electron microscope (TEM) collection of illustrative plates of 4 kinds of samples, and wherein scheming a is TiO
2, figure b is TiO
2/ (1.5%) rGO, figure c is TiO
2/ (3.0%) rGO, figure d is TiO
2/ (4.5%) rGO.
Fig. 3 is 4 kinds of sample specific 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 be the XPS of 4 kinds of samples entirely compose each element in (each element see in figure a mark above dotted line) and four kinds of samples containing scale, figure b is TiO
2the high-resolution XPS collection of illustrative plates of C 1s in/(1.5%) rGO, figure c is TiO
2the high-resolution XPS collection of illustrative plates of C 1s in/(3.0%) rGO, figure d is TiO
2the high-resolution XPS collection of illustrative plates of C 1s in/(4.5%) rGO, figure e is TiO
2the high-resolution XPS collection of illustrative plates of N 1s in/rGO, figure f is TiO
2the high-resolution XPS collection of illustrative plates of F 1s in/rGO;
Cyclic voltammetry curve (CV) figure that Fig. 6 is four kinds of samples in oxygen and the saturated 0.1 M KOH solution of nitrogen, illustration a is TiO
2, figure b is TiO
2/ (1.5%) rGO, figure c is TiO
2/ (3.0%) rGO, figure d is TiO
2/ (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 separately time m-electric current (i-t) curve; Wherein time m-electric current (i-t) curve of 3 kinds of samples almost overlaps;
Rotating disk electrode (r.d.e) (RED) curve map that Fig. 9 is the lower 3 kinds of samples of room temperature in the saturated 0.1 M KOH solution of oxygen, the electro transfer number that illustration is Koutechy-Levich curve map under different electromotive force and calculates; Wherein scheming a is TiO
2/ (1.5%) rGO, figure b is TiO
2/ (3.0%) rGO, figure c is TiO
2/ (4.5%) rGO;
Rotating ring disk electrode (r.r.d.e) (RRED) curve map 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, figure b is that 3 kinds of samples generate H in electrochemistry experiment
2o
2percentage composition, illustration is the electron transfer number of 3 kinds of samples;
In Fig. 1-10 mark TiO
2for modified Nano TiO prepared in comparative example 1
2;
Figure 11 is that the present invention of hydro-thermal one pot process possesses efficient electric catalytic oxidation-reduction performance TiO
2preparation technology's schematic diagram of/rGO composite.
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), slowly add raw material butyl titanate 10.00mL, stir 5 min, form light yellow transparent liquid, add ammonium fluoride 0.867 gram, 1.406 grams, urea, graphene oxide 2mL (1g/100mL), be stirred to solution clarification (about 5 min), last hydrochloric acid 16.00 mL dropwise adding 6mol/L, after abundant stirring, reaction solution is proceeded in the autoclave of 100mL, be heated to 200 DEG C, constant temperature took out after 10 hours, product is with absolute ethanol washing three times, again with second distillation water washing three times, to put at vacuum distillation apparatus 50 DEG C decompression distillation 20 minutes, obtain the pulverulent solids of black, be the TiO possessing efficient electric catalytic oxidation-reduction performance
2/ rGO composite---TiO
2/ (1.5%) rGO.
Characterize through SEM and 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 area of material is 207.8 m
2/ g.Raman (RM) spectrum test shows, graphene oxide (GO) is reduced to redox graphene (rGO) in Hydrothermal Synthesis process, and the ratio at D peak and G peak is I
d/ I
g=1.29.XPS shows, containing N, F, O, Ti, C in composite, wherein the content of N and F element is all at about 1.0 %, the content of rGO is at about 1.5 %, compared with graphene oxide, in the material with carbon element of redox graphene, oxydant significantly reduces, and the graphene oxide in further testimonial material is reduced to redox graphene.Cyclic voltammetry (CV) result shows, composite is in the saturated 0.1 M KOH solution of oxygen, have high electrocatalytic oxidation reducing property, initial oxidation current potential is at about-0.2 V, and recording maximum oxygen reduction current according to the Tafel curve of material can reach 3.35 × 10
-6mA cm
-2.Chronoamperometry (i-t) experimental result shows, through 16, after after the electro-chemical test of 000 s, and about 91 % when current density of this material is initial.The test result of rotating disk electrode (r.d.e) (RDE) and rotating ring disk electrode (r.r.d.e) (RRDE) shows that this material is selective four very high electron reaction systems to the reaction of hydrogen reduction.
Embodiment 2
In the small beaker of 50mL, while magnetic stirrer, add 10.00mL absolute ethyl alcohol, 3.00mL ethylene glycol stoste, slowly add raw material butyl titanate 10.00mL, stir 5min, form light yellow transparent liquid, add ammonium fluoride 0.867 gram, 1.406 grams, urea, graphene oxide 4mL (1g/100mL), be stirred to solution clarification (about 5 min), last hydrochloric acid 16.00 mL dropwise adding 6mol/L, after abundant stirring, reaction solution is proceeded in the autoclave of 100 mL, be heated to 200 DEG C, constant temperature took out after 10 hours, product is with absolute ethanol washing three times, again with second distillation water washing three times, to put at vacuum distillation apparatus 50 DEG C decompression distillation 20 minutes, obtain the pulverulent solids of black, be the TiO possessing efficient electric catalytic oxidation-reduction performance
2/ rGO composite---TiO
2/ (3.0%) rGO.
Characterize through SEM and 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 area of material is 316.2 m
2/ g.Raman (RM) spectrum test shows, graphene oxide (GO) is reduced to redox graphene (rGO) in Hydrothermal Synthesis process, and the ratio at D peak and G peak is I
d/ I
g=1.35.XPS shows, containing N, F, O, Ti, C in composite, wherein the content of N and F element is all at about 1.0 %, the content of rGO is at about 3.0 %, compared with graphene oxide, in the material with carbon element of redox graphene, oxydant significantly reduces, and the graphene oxide in further testimonial material is reduced to redox graphene.Cyclic voltammetry (CV) result shows, composite is in the saturated 0.1 M KOH solution of oxygen, have high electrocatalytic oxidation reducing property, initial oxidation current potential is at about-0.2 V, and recording maximum oxygen reduction current according to the Tafel curve of material can reach 1.29 × 10
-5mA cm
-2.Chronoamperometry (i-t) shows, through 16, after the electrochemistry experiment of 000 s, and about 92 % when current density of this material is initial.The test of rotating disk electrode (r.d.e) (RDE) and rotating ring disk electrode (r.r.d.e) (RRDE) shows that this material is selective four very high electron reaction systems to the reaction of hydrogen reduction.
Embodiment 3
In the small beaker of 50mL, while magnetic stirrer, add 10.00mL absolute ethyl alcohol, 3.00mL ethylene glycol stoste, slowly add raw material butyl titanate 10.00mL, stir 5min, form light yellow transparent liquid, add ammonium fluoride 0.867 gram, 1.406 grams, urea, graphene oxide 6mL (1g/100mL) fully agitating solution extremely clarification (about 5 min), the last hydrochloric acid 16.00mL dropwise adding 6mol/L, after abundant stirring, reaction solution is proceeded in the autoclave of 100ml, be heated to 200 DEG C, constant temperature took out after 10 hours, product is with absolute ethanol washing three times, again with second distillation water washing three times, to put at vacuum distillation apparatus 50 DEG C decompression distillation 20 minutes, obtain the pulverulent solids of black, be the TiO possessing efficient electric catalytic oxidation-reduction performance
2/ rGO composite---TiO
2/ (4.5%) rGO.
Characterize through SEM and 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 area of material is 382.2 m
2/ g.Raman (RM) spectrum test shows, graphene oxide (GO) is reduced to redox graphene (rGO) in Hydrothermal Synthesis process, and the ratio at D peak and G peak is I
d/ I
g=1.31.XPS shows, containing N, F, O, Ti, C in composite, wherein the content of N and F element is all at about 1.0 %, the content of rGO is at about 4.5 %, compared with graphene oxide, in the material with carbon element of redox graphene, oxydant significantly reduces, and the graphene oxide in further testimonial material is reduced to redox graphene.Cyclic voltammetry (CV) result shows, composite is in the saturated 0.1 M KOH solution of oxygen, have high electrocatalytic oxidation reducing property, initial oxidation current potential is at about-0.2 V, and recording maximum oxygen reduction current according to the Tafel curve of material can reach 5.74 × 10
-6mA cm
-2.Chronoamperometry (i-t) shows, through 16, after the electrochemistry experiment of 000 s, and about 90 % when current density of this material is initial.The test of rotating disk electrode (r.d.e) (RDE) and rotating ring disk electrode (r.r.d.e) (RRDE) shows that this material is selective four very high electron reaction systems to the reaction of hydrogen reduction.
Comparative example 1
In the small beaker of 50mL, while magnetic stirrer, add 10.00mL absolute ethyl alcohol, 3.00mL ethylene glycol stoste, slowly add raw material butyl titanate 10.00mL, stir 10min, form light yellow transparent liquid, add ammonium fluoride 0.867 gram, 1.406 grams, urea, be stirred to solid particle to dissolve completely, the last hydrochloric acid 16.00ml dropwise adding 6mol/L, after being stirred to solution clarification, reaction solution is proceeded in the autoclave of 100mL, be heated to 200 DEG C, constant temperature took out after 10 hours, product is with absolute ethanol washing three times, again with second distillation water washing three times, to put at vacuum distillation apparatus 50 DEG C decompression distillation 20 minutes, obtain flaxen pulverulent solids, be N element and F element is successfully doped to nano-TiO
2the Anatase modified Nano TiO of N, F codope of lattice
2particle.
Characterize through SEM and TEM, modified nano-titanium dioxide particle, particle diameter is 5 ± 2 nm.BET outcome research proves, the specific area of material is 124.6 m
2/ g.XPS shows, containing N, F, O, Ti, C in composite, wherein the content of N and F element is all about 1%, and C element derives from the carbon contamination in instrument test.Cyclic voltammetry (CV) result shows, this material in the saturated 0.1 M KOH solution of oxygen, without 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, is platinum electrode to electrode, and 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 kind
2the method of/rGO composite, comprises butyl titanate, graphene oxide, absolute ethyl alcohol, ethylene glycol, urea and ammonium fluoride, the step of constant temperature 8-12 hour under pH=1-4, T=190-230 DEG C of condition.
2. method according to claim 1, is characterized in that,
Butyl titanate, absolute ethyl alcohol, ethylene glycol add in reactor, be stirred to and form faint yellow settled solution, then add urea, ammonium fluoride and graphene oxide, with the salt acid for adjusting pH of 6mol/L, be stirred to solution clarification after in 200 DEG C, isothermal reaction was cooled to room temperature after 10 hours; Product is washed twice above with redistilled water again after product absolute ethanol washing more than twice, then decompression distillation.
3. method according to claim 1 and 2, is characterized in that, the mol ratio of graphene oxide and butyl titanate is 1.5-4.5:100.
4. method according to claim 1 and 2, is characterized in that, the mol ratio of urea, ammonium fluoride and butyl titanate is 1:100.
5. method according to claim 1 and 2, is characterized in that, the volume ratio of butyl titanate, absolute ethyl alcohol and ethylene glycol is 10:10:3.
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101890344A (en) * | 2010-07-27 | 2010-11-24 | 华东理工大学 | Preparation method of graphene/titanium dioxide composite photocatalyst |
KR20110098388A (en) * | 2010-02-26 | 2011-09-01 | 전남대학교산학협력단 | Preparation method of carbon material based photocatalyst with improved photo catalytic activity, the photocatalyst prepared by the former method and the filter containing the former carbon material based photo catalyst |
CN102380364A (en) * | 2011-09-02 | 2012-03-21 | 武汉大学 | Preparation method of TiO2/graphene composite film |
TW201223861A (en) * | 2010-12-08 | 2012-06-16 | Taiwan Textile Res Inst | Graphene/nano-TiO2 composites and method for preparing the same |
KR20120079401A (en) * | 2011-01-04 | 2012-07-12 | 이화여자대학교 산학협력단 | Porous graphene-layered titanium oxide nanohybrids and production method thereof |
CN103007977A (en) * | 2012-12-25 | 2013-04-03 | 济南大学 | Preparation method of modified TiO2 with visible light response |
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 |
CN103521252A (en) * | 2013-10-30 | 2014-01-22 | 苏州大学 | Photocatalyst of N-doped graphene compound semiconductor nano particles and preparation method thereof |
-
2015
- 2015-02-10 CN CN201510069023.2A patent/CN104624220B/en not_active Expired - Fee Related
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20110098388A (en) * | 2010-02-26 | 2011-09-01 | 전남대학교산학협력단 | Preparation method of carbon material based photocatalyst with improved photo catalytic activity, the photocatalyst prepared by the former method and the filter containing the former carbon material based photo catalyst |
CN101890344A (en) * | 2010-07-27 | 2010-11-24 | 华东理工大学 | Preparation method of graphene/titanium dioxide composite photocatalyst |
TW201223861A (en) * | 2010-12-08 | 2012-06-16 | Taiwan Textile Res Inst | Graphene/nano-TiO2 composites and method for preparing the same |
KR20120079401A (en) * | 2011-01-04 | 2012-07-12 | 이화여자대학교 산학협력단 | Porous graphene-layered titanium oxide nanohybrids and production method thereof |
CN102380364A (en) * | 2011-09-02 | 2012-03-21 | 武汉大学 | Preparation method of TiO2/graphene composite film |
CN103007977A (en) * | 2012-12-25 | 2013-04-03 | 济南大学 | Preparation method of modified TiO2 with visible light response |
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 |
CN103521252A (en) * | 2013-10-30 | 2014-01-22 | 苏州大学 | Photocatalyst of N-doped graphene compound semiconductor nano particles and preparation method thereof |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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CN109718752B (en) * | 2019-01-27 | 2021-11-12 | 安徽大学 | graphene/TiO2Nanocomposite and method for preparing same |
CN113130884A (en) * | 2021-04-07 | 2021-07-16 | 福建大成新能源科技有限公司 | F-doped TiO2Preparation method and application of (E) -B |
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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