CN102107147A - Titanium dioxide and carbon composite material, preparation and application thereof - Google Patents
Titanium dioxide and carbon composite material, preparation and application thereof Download PDFInfo
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- CN102107147A CN102107147A CN2010106014584A CN201010601458A CN102107147A CN 102107147 A CN102107147 A CN 102107147A CN 2010106014584 A CN2010106014584 A CN 2010106014584A CN 201010601458 A CN201010601458 A CN 201010601458A CN 102107147 A CN102107147 A CN 102107147A
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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
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- 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 provides a titanium dioxide (TiO2) and carbon composite material, which belongs to the technical field of composite materials. The composite material is obtained by graphitizing TiO2/Ppy which is modified by polypyrrole (Ppy) and used as a precursor. The composite material has the characteristics of high activity, large specific surface area and the like. Nitrogen atoms provided by TiO2 and pyrrole in the composite material and active metal particles (such as Pt) can generate synergistic effect; meanwhile, the active particles can be better dispersed to promote the catalytic activity of the metal particles; the nitrogen atoms on the surface can be used for fixing active particles of a catalyst, so problems that the active particles fall during catalysis can be reduced, and the service life is prolonged; furthermore, the TiO2 nanoparticles have a strong anti-corrosion effect, so the stability of the catalyst can be enhanced. Therefore, the composite material can be used as a catalyst carrier for preparing a fuel cell electrode catalyst.
Description
Technical field
The invention belongs to technical field of composite materials, relate to a kind of titanium dioxide-carbon composite and preparation method thereof; The invention still further relates to this titanium dioxide-carbon composite as the application of carrier in the preparation electrode catalyst of fuel cell.
Background technology
Be a kind of chemical energy that will be present in fuel and the oxidant, isothermal, efficient, the eco-friendly TRT that is converted into electric energy.In addition advantages such as it is little to have discharging, and energy transformation ratio height, storage and transportation safety are convenient, noise is low, also have original advantage: normal temperature uses, fuel carry supply convenient, do not have a machinery vibration etc.Fuel cell is the environmental protection after waterpower, firepower, Chemically generation, the most reliable generation mode, in every field splendid potential application foreground is arranged.
Fuel-cell catalyst is the important component part of fuel cell, and it directly influences fuel cell performance, efficient and stability.The Pt/C catalyst is the commercial catalysts of comparative maturity, and hydrogen reduction is had higher activity, and stability is preferably arranged in sour environment.Pt/C is a carrier with the Vulcan-XC72 that Cabot company produces, but Vulcan-XC72 reunites easily, therefore easily the Pt atom with catalytic activity is coated in the Pt/C catalyst of preparation, make catalytic active center reduce, reduced the catalytic performance of catalyst; The catalytic activity of Vulcan-XC72 itself is low in addition, has also more reduced the performance of catalyst.In addition, between Pt and the C active force a little less than, cause Pt to come off easily, and temperature, pH variation can cause the corrosion of C, also reduce activity of such catalysts.
Therefore, the development of fuel-cell catalyst be unable to do without the active metal particles of research various combination, also be unable to do without the new carrier of research.Select the surface to contain the carrier of active group or atom, can improve activity of such catalysts, improve the stability of catalyst.In recent years, people prepare the carrier that catalyst adopts and develop into nanometer rods, nanofiber pipe, metal oxide etc. from traditional carbon powder carrier.The methods such as degree of graphitization that recent findings is modified carrier or raising carrier with heteroatom can be used to prepare the carrier of high activity, high stability, thereby prepare highly active catalyst.
Titanium dioxide is a kind of semiconductor, have special photoelectron effect, stable especially in acid solution, and can produce cooperative effect between titanium dioxide and the Pt, utilize these character of titanium dioxide can strengthen the corrosion resistance of catalyst, improve activity of such catalysts simultaneously.
One of donor of nitrogen-atoms commonly used is a polypyrrole, after the polypyrrole graphitization processing, can form the nitrogen doped graphite layer with high conductivity, improves the electric conductivity of carrier and the dispersion of active particle, thereby can improve activity of such catalysts.
Summary of the invention
The objective of the invention is to utilize the character of titanium dioxide and polypyrrole, a kind of high-activity titanium deoxide-carbon composite that has is provided in order to overcome problems of the prior art.
Another object of the present invention provides a kind of preparation method of high-activity titanium deoxide-carbon composite.
A further object of the invention, just providing a kind of is the method for preparing carriers electrode catalyst of fuel cell with this high-activity titanium deoxide-carbon composite.
The preparation method of titanium dioxide-carbon composite of the present invention is that titanium dioxide nano-particle and the pyrrole monomer mass ratio with 1:1 ~ 1:5 is added to the water, and stirs it is mixed; Add the surfactant of 1 ~ 10 times of pyrrole monomer quality again, it is even to continue to be stirred to surfactant-dispersed, adds oxidizing agent solution again, reacts 20 ~ 24 h down in 0 ~ 5 ℃; After reaction is finished, suction filtration, drying gets titanium dioxide/polypyrrole precursor.In nitrogen environment, titanium dioxide/polypyrrole precursor in 600 ~ 1000 ℃ of graphitization processing 2 ~ 6 h, is got titanium dioxide-carbon composite then.
Described surfactant is octadecyl trimethylammonium bromide, softex kw or neopelex.
Described oxidizing agent solution is the FeCl of mass concentration 5 ~ 25 %
3(the NH of solution or mass concentration 1 ~ 20 %
4)
2S
2O
8Solution; Wherein the amount of oxidant is 1 ~ 8 times of pyrrole monomer quality.
Titanium dioxide-the carbon composite of the present invention's preparation is to be matrix with titanium dioxide, and with the graphitization product of polypyrrole modifying, it has characteristics such as activity is high, specific area is big.The nitrogen-atoms that titanium dioxide and pyrroles provide in the composite can produce cooperative effect with active metal particles (as Pt), simultaneously active particle is better disperseed, and promotes the catalytic activity of metallic; The nitrogen-atoms on surface can the fixed catalyst active particle, reduces problems such as active particle coming off in catalytic process, improves service life; In addition, titanium dioxide nano-particle has strong corrosion-resistant effect, can increase the stability of catalyst.Therefore, can be used as catalyst carrier and be used to prepare electrode catalyst of fuel cell.
The preparation method of composite loaded Pt catalyst of the present invention is as follows:
The natrium citricum that adds 1 ~ 4 times of chloroplatinic acid and chloroplatinic acid quality in ethylene glycol ultrasonicly dissolves it fully; Regulate PH=8 ~ 11 with the KOH/ ethylene glycol solution, add the titanium dioxide-carbon composite of 1 ~ 5 times of chloroplatinic acid quality again, stir ultrasonic 0.1 ~ 0.5 h down, then in 60 ~ 180 ℃ of back flow reaction 4 ~ 10 h; Suction filtration, washing is dried to weight, gets loaded Pt catalyst.
Below the structure of the catalyst of the structure of titanium dioxide-carbon composite and supporting Pt and the performance of catalyst are tested.
Fig. 1 is TiO
2, TiO
2/ Ppy(titanium dioxide-polypyrrole), TiO
2-CN
x(titanium dioxide-carbon composite) and Pt/TiO
2-CN
xX-ray diffraction (XRD) figure of (titanium dioxide-carbon composite carrier load Pt catalyst).Four of Pt crystal faces are respectively (111) among Fig. 1, (200), (220) and (311), TiO
2And TiO
2-CN
xCompare TiO when diffraction maximum is 24 °
2-CN
xThe peak obviously broaden, this is because carbon (002) crystal face and TiO
2(101) crystal face stack.TiO
2And TiO
2/ Ppy compares, since the covering of Ppy, TiO
2TiO among the/Ppy
2Feature crystal face peak weaken.Titanium dioxide (the TiO that has successfully prepared polypyrrole modifying is described
2/ Ppy) precursor.
For the catalytic performance of titanium dioxide-carbon composite carrier load Pt catalyst is tested, at 0.5 M H
2SO
4Carried out the cyclic voltammetric test in the solution, and with commercial Pt/C(20%wt) catalyst compares.Fig. 2 is commercial Pt/C(20%wt) and Pt/TiO
2-CN
xAt the saturated 0.5M H of nitrogen
2SO
4Cyclic voltammetric resolution chart in the solution.Got by the dehydrogenation zone calculated activity area among Fig. 2: Pt/C is 27.6 m
2g
-1, Pt/TiO
2-CN
xBe 41.5 m
2g
-1The TiO of the present invention's preparation is described
2-CN
xThe composite loaded Pt catalyst is compared 20 %wt Pt/C catalyst, and the dispersiveness of active metal particles is improved significantly.Fig. 3 is commercial Pt/C(20%wt) and the catalyst Pt/TiO of complex carrier preparation
2-CN
xAt 0.5 M H
2SO
4Hydrogen reduction polarization curve in the solution.From Fig. 3, calculate Pt/TiO
2-CN
xTake-off potential and half wave potential respectively than commercial Pt/C(20%wt) high 25mV and 18mV.Complex carrier TiO is described
2-CN
xCompare the traditional C carrier hydrogen reduction is had obvious facilitation.Fig. 4 is commercial Pt/C(20%wt) and Pt/TiO
2-CN
xCatalyst is the unit platinum mass activity current density column schematic diagram when 0.85V and 0.8V in oxygen reduction reaction.Find out that by Fig. 4 Pt/C(20%wt) the unit platinum mass activity current density size of catalyst when 0.8 V and 0.85 V is respectively: 0.47 mA mg
-1With 0.25 mA mg
-1, and Pt/TiO
2-CN
xCatalyst is up to 0.51 mA mg
-1With 0.34 mA mg
-1, improve 8% and 36% than Pt/C catalyst respectively.Fig. 5 is Pt/C(20%wt) and Pt/TiO
2-CN
xThe Tafel curve.Fig. 5 demonstrates Pt/TiO
2-CN
xThe dynamics electric current significantly greater than Pt/C.
In sum, the present invention prepares the activity of such catalysts height for preparing after titanium dioxide-carbon composite supporting Pt, the good dispersion of active particle, in the hydrogen reduction process, has good catalytic activity, and good stability, long service life, so titanium dioxide-carbon composite is a kind of fuel-cell catalyst carrier preferably.
Description of drawings
Fig. 1 is TiO
2, TiO
2/ Ppy, TiO
2-CN
xAnd Pt/TiO
2-CN
xX-ray diffraction pattern.
Fig. 2 is commercial Pt/C(20%wt) and Pt/TiO
2-CN
xCatalyst is at 0.5 M H
2SO
4In the solution cyclic voltammetric resolution chart (reference electrode is the Ag/AgCl electrode).
Fig. 3 is commercial Pt/C(20%wt) and Pt/TiO
2-CN
xThe hydrogen reduction polarization curve of catalyst (reference electrode is the Ag/AgCl electrode).
Fig. 4 is commercial Pt/C(20%wt) and Pt/TiO
2-CN
xCatalyst is the unit platinum mass activity current density column schematic diagram (reference electrode is the Ag/AgCl electrode) when 0.85 V and 0.8 V in oxygen reduction reaction.
Fig. 5 is commercial Pt/C(20%wt) and Pt/TiO
2-CN
xThe Tafel figure (reference electrode is the Ag/AgCl electrode) of catalyst.
The specific embodiment
Below by specific embodiment composite of the present invention and corresponding Preparation of catalysts thereof are described further.
Embodiment 1
(1) titanium dioxide/carbon composite (TiO
2-CN
x) preparation
In 250 ml round-bottomed flasks, add 0.4g TiO
2(particle diameter is 10 ~ 20nm) and the distilled water of 60 ml to nano particle, stirs; Add 0.4 g pyrrole monomer, continue to stir, add 3 g neopelexes again, the aqueous solution that slowly drips iron chloride then (wherein contains iron chloride 2 g, three distilled water 10 ml), react 20 h in 0 ~ 5 ℃: after reaction is finished, suction filtration, 70 ℃ of drying 10 h get titanium dioxide/polypyrrole precursor.
Titanium dioxide/polypyrrole precursor is placed tube furnace, under nitrogen protection,, get titanium dioxide/carbon composite (TiO in 600 ℃ of heat treatment 4 h
2-CN
x).
(2) the corresponding Preparation of Catalyst of load platinum
Chloroplatinic acid 50 mg are joined in the 100 ml round-bottomed flasks, add 22 ml ethylene glycol, and add the magneton stirring, it was dissolved fully in ultrasonic 0.5 hour in stirring down; Add 120 mg natrium citricums again, be stirred to dissolving fully; With PH=9 of KOH/EG solution regulator solution, add titanium dioxide/carbon composite (TiO of above-mentioned preparation then
2-CN
x) 100 mg, stirred 0.5 hour earlier, behind ultrasonic again 0.1 h, at 160 ℃ of back flow reaction 6 h.Gained solution suction filtration, with three water washings, 60 ℃ are dried to weight promptly.
In prepared catalyst, active particle Pt and carrier TiO
2-CN
xMass ratio be 1:3.
Pt/TiO
2-CN
xThe current density that the unit mass metal produced when catalyst was 0.8V at voltage is 0.526mA mg
-1 Pt, commercial Pt/C catalyst improves 12 %.
(1) titanium dioxide/carbon composite (TiO
2-CN
x) preparation
In 250 ml round-bottomed flasks, add 0.5 g TiO
2(particle diameter is 10 ~ 20nm) and the distilled water of 60 ml to nano particle, stirs; Add 1 g pyrrole monomer,, add 4 g octadecyl trimethylammonium bromides again, slowly drip the aqueous solution (wherein containing iron chloride 2 g, three distilled water 10 ml) of iron chloride then, react 22 h in 0 ~ 5 ℃: after the reaction, suction filtration, 80 ℃ of drying 10 h get titanium dioxide/polypyrrole precursor.
Titanium dioxide/polypyrrole precursor is placed tube furnace, under nitrogen protection,, get titanium dioxide/carbon composite (TiO in 800 ℃ of graphitization processing 4 h
2-CN
x).
(2) the corresponding Preparation of Catalyst of load platinum
Chloroplatinic acid 68 mg are joined in the 100 ml round-bottomed flasks, add 30 ml ethylene glycol, and add the magneton stirring, it is dissolved fully in stirring is ultrasonic down; Add 100 mg natrium citricums again, be stirred to dissolving fully; With PH=8 of KOH/EG solution regulator solution, add titanium dioxide/carbon composite (TiO of above-mentioned preparation then
2-CN
x) 150 mg, stirred 0.5 hour, ultrasonic again 0.2 hour, in 100 ℃ of back flow reaction 6 h.Gained solution suction filtration, with three water washings, 60 ℃ are dried to weight.
In prepared catalyst, active particle Pt and carrier TiO
2-CN
xMass ratio be 1:6.
Pt/TiO
2-CN
xThe current density that the unit mass metal produced when catalyst was 0.8V is 0.547mA mg
-1 Pt, commercial Pt/C catalyst improves 15 %.
Embodiment 3
(1) titanium dioxide/carbon composite (TiO
2-CN
x) preparation
In 250 ml round-bottomed flasks, add 0.2g TiO
2The distilled water of nano particle and 60ml stirs; Add the 1g pyrrole monomer, add the 2g softex kw again, the aqueous solution that slowly drips ammonium persulfate then (wherein contains ammonium persulfate 0.6 g, distilled water 10 ml), react 24 h in 0 ~ 5 ℃: after reaction is finished, suction filtration, 60 ℃ of drying 10 h get titanium dioxide/polypyrrole precursor.
Titanium dioxide/polypyrrole precursor is placed tube furnace, under nitrogen protection, in 1000 ℃ of graphitization processing 2 hours, titanium dioxide/carbon composite (TiO
2-CN
x).
(2) the corresponding Preparation of Catalyst of load platinum
In prepared catalyst, active particle Pt and carrier TiO
2-CN
xMass ratio be 1:8.
Pt/TiO
2-CN
xThe current density that the unit mass metal produced when catalyst was 0.8V is 0.515mA mg
-1 Pt, commercial Pt/C catalyst improves 9 %.
Claims (6)
1. the preparation method of a titanium dioxide-carbon composite is that titanium dioxide nano-particle and the pyrrole monomer mass ratio with 1:1 ~ 1:5 is added to the water, and stirs it is mixed; The surfactant that adds 1 ~ 10 times of pyrrole monomer quality again is stirred to and is uniformly dispersed; Add oxidizing agent solution then, react 20 ~ 24h down in 0 ~ 5 ℃; After reaction is finished, suction filtration, drying gets titanium dioxide/polypyrrole precursor; Under nitrogen protection,, get titanium dioxide-carbon composite at last with titanium dioxide/polypyrrole precursor graphitization processing 2 ~ 6 h under 600 ~ 1000 ℃ high temperature.
2. the preparation method of titanium dioxide-carbon composite according to claim 1, it is characterized in that: described surfactant is octadecyl trimethylammonium bromide, softex kw or neopelex.
3. the preparation method of titanium dioxide-carbon composite according to claim 1, it is characterized in that: the particle diameter of described titanium dioxide nano-particle is 10 ~ 20nm.
4. the preparation method of titanium dioxide-carbon composite according to claim 1, it is characterized in that: described oxidizing agent solution is the FeCl of mass concentration 5 ~ 25 %
3(the NH of solution or mass concentration 1 ~ 20 %
4)
2S
2O
8Solution; The amount of oxidant is 1 ~ 8 times of pyrrole monomer quality.
According to claim 1 titanium dioxide-the carbon composite of method preparation as the application of carrier in the preparation electrode catalyst of fuel cell.
According to claim 1 titanium dioxide-the carbon composite of method preparation as the application of carrier in the preparation electrode catalyst of fuel cell, it is characterized in that: in ethylene glycol, add the natrium citricum of 1 ~ 4 times of chloroplatinic acid and chloroplatinic acid quality, ultrasonic it is disperseed fully; Regulate PH=8 ~ 11 with the KOH/ ethylene glycol solution, add the titanium dioxide-carbon composite of 1 ~ 5 times of chloroplatinic acid quality again, stirred ultrasonic 0.1 ~ 0.5 hour, then in 60 ~ 180 ℃ of back flow reaction 4 ~ 10 h; Suction filtration, washing is dried to weight, gets titanium dioxide-carbon and carries the Pt catalyst.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102728398A (en) * | 2012-06-18 | 2012-10-17 | 华东师范大学 | Preparation method for ordered mesoporous non-noble metal-nitrogen-graphitized carbon material |
| CN102744068A (en) * | 2012-07-20 | 2012-10-24 | 常州大学 | Magnetic-separable titanium dioxide P25-ferrite-graphene nanometer catalyst and preparation method thereof |
| CN103915608A (en) * | 2014-04-14 | 2014-07-09 | 惠州市汉派电池科技有限公司 | Negative electrode material for lithium ion power battery, preparation method and application of negative electrode material |
| CN104992846A (en) * | 2015-06-29 | 2015-10-21 | 温州大学 | Hetero-atom doped titanium composite material, and preparation method and application thereof |
| CN105591090A (en) * | 2016-03-04 | 2016-05-18 | 河源广工大协同创新研究院 | Preparation method of zinc oxide/nitrogen-doped carbon composite material capable of being used for lithium ion battery negative electrode |
| CN111584888A (en) * | 2020-05-27 | 2020-08-25 | 湖南大学 | Preparation method of silicon dioxide doped/coated platinum-carbon catalyst |
| CN112421053A (en) * | 2020-11-23 | 2021-02-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nano composite material for fuel cell cathode catalyst |
| CN113087014A (en) * | 2021-03-31 | 2021-07-09 | 杭州艺深新材料有限公司 | Preparation method of carbon/selenium-doped titanium dioxide lithium-sulfur battery positive electrode material |
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| CN101716530A (en) * | 2009-11-25 | 2010-06-02 | 武汉理工大学 | Catalyst using composite polymer as carrier |
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| WO2009035214A1 (en) * | 2007-09-12 | 2009-03-19 | Samsung Electronics Co., Ltd. | Graphene shell and process of preparing the same |
| CN101696109A (en) * | 2009-10-19 | 2010-04-21 | 青岛科技大学 | Method for preparing mesoporous titanium dioxide microspheres |
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|---|---|---|---|---|
| CN102728398B (en) * | 2012-06-18 | 2013-12-25 | 华东师范大学 | Preparation method for ordered mesoporous non-noble metal-nitrogen-graphitized carbon material |
| CN102728398A (en) * | 2012-06-18 | 2012-10-17 | 华东师范大学 | Preparation method for ordered mesoporous non-noble metal-nitrogen-graphitized carbon material |
| CN102744068A (en) * | 2012-07-20 | 2012-10-24 | 常州大学 | Magnetic-separable titanium dioxide P25-ferrite-graphene nanometer catalyst and preparation method thereof |
| CN103915608A (en) * | 2014-04-14 | 2014-07-09 | 惠州市汉派电池科技有限公司 | Negative electrode material for lithium ion power battery, preparation method and application of negative electrode material |
| CN103915608B (en) * | 2014-04-14 | 2015-07-22 | 凤凰新能源(惠州)有限公司 | Negative electrode material for lithium ion power battery, preparation method and application of negative electrode material |
| CN104992846B (en) * | 2015-06-29 | 2017-11-14 | 温州大学 | A kind of Heteroatom doping titanium composite material and preparation method thereof and purposes |
| CN104992846A (en) * | 2015-06-29 | 2015-10-21 | 温州大学 | Hetero-atom doped titanium composite material, and preparation method and application thereof |
| CN105591090A (en) * | 2016-03-04 | 2016-05-18 | 河源广工大协同创新研究院 | Preparation method of zinc oxide/nitrogen-doped carbon composite material capable of being used for lithium ion battery negative electrode |
| CN105591090B (en) * | 2016-03-04 | 2018-06-05 | 河源广工大协同创新研究院 | A kind of preparation method of zinc oxide/nitrogen-doped carbon composite material available for negative electrode of lithium ion battery |
| CN111584888A (en) * | 2020-05-27 | 2020-08-25 | 湖南大学 | Preparation method of silicon dioxide doped/coated platinum-carbon catalyst |
| CN112421053A (en) * | 2020-11-23 | 2021-02-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nano composite material for fuel cell cathode catalyst |
| CN112421053B (en) * | 2020-11-23 | 2022-09-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nano composite material for fuel cell cathode catalyst |
| CN113087014A (en) * | 2021-03-31 | 2021-07-09 | 杭州艺深新材料有限公司 | Preparation method of carbon/selenium-doped titanium dioxide lithium-sulfur battery positive electrode material |
| CN113087014B (en) * | 2021-03-31 | 2022-07-01 | 江西普瑞森新能源科技有限公司 | Preparation method of carbon/selenium-doped titanium dioxide lithium-sulfur battery positive electrode material |
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