CN1253245C - Method of depositing high density loading metal platinum on carbon nanometer pipe surface using oriented chemistry - Google Patents
Method of depositing high density loading metal platinum on carbon nanometer pipe surface using oriented chemistry Download PDFInfo
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- CN1253245C CN1253245C CN 200410008326 CN200410008326A CN1253245C CN 1253245 C CN1253245 C CN 1253245C CN 200410008326 CN200410008326 CN 200410008326 CN 200410008326 A CN200410008326 A CN 200410008326A CN 1253245 C CN1253245 C CN 1253245C
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Abstract
The present invention relates to a new method for carrying metal platinum on the surfaces of carbon nano-tubes through orientated deposition. The carbon nano-tubes, chloride of platinum and surface active agents react in polyalcohol according to a ratio that each liter of polyalcohol mixed solution contains 0.1 to 10g of carbon nano-tube, 1 to 100g of surface active agent and 0.05 to 10g of platinum measured by the platinum content in metal salts, the oriented chemical deposition of nanometer platinum particles on the surfaces of the carbon nano-tubes is realized, and the problem of self agglomeration of metal particles is solved. The high carrying rate of platinum is realized, and the distribution is uniform. Dense nanometer platinum particle layers can be obtained at high carrying rate (more than 50%), the average particle size is 5 nm, and the size distribution is narrow. The prepared carbon nano-tubes surface carried nanometer metal platinum particle catalysts have much better electrocatalytic performance to methanol oxidation reactions than that of the similar commercial catalysts E-TEK, and can be used for electrocatalysts of fuel cells, other catalytic fields, etc.
Description
Technical field
The present invention relates to a kind of new method that is deposited on the carbon nano tube surface loaded metal platinum by directed chemistry.
Background technology
Since Iijima in 1991 finds CNT, because optics, electricity, magnetics and the mechanical performance of its particular structure, excellence, CNT has caused people's extensive studies interest. the application of CNT has related to field (Baughman R.H. such as composite, FED, scanning microprobe needle point, nanometer electronic device, Chu Qing and catalyst carrier, et al, Science, 2002,297:787).Because CNT is the one-dimensional material with higher length diameter ratio (diameter is in tens nanometers, and length is that several microns are to a hundreds of micron) and hollow structure, therefore can make the one dimension composite of template for preparing novelty of it.For example utilize the capillarity of CNT some element can be packed in the pipe, also can coat the carbon mitron, can obtain having one-dimensional material (the van Bommel K.J.C. of special nature with different materials, et al, Angew.Chem.Int.Ed., 2003,42:980).
The method of supported precious metal nano-particle mainly contains two classes on CNT at present: infusion process and self-assembly method.Infusion process is that CNT is mixed with the solution of slaine, the dipping a period of time after with the solvent evaporate to dryness, again slaine is added thermal decomposition, reducing metal (Planeix under nitrogen atmosphere then, J.M., et al, J.Am.Chem.Soc., 1994,116:7935), perhaps thereby metal ion is reduced agent at solution and is reduced into metal and is deposited on and obtain Nano carbon tube-metal compound (LiWZ on the carbon nano tube surface, et al, J.Phys.Chem.B, 2003,107:6292), this method is widely used in the preparation of carbon nanotube loaded metallic catalyst.The shortcoming of this method is that carbon nano tube surface is difficult to obtain the even metal cover layer, and a large amount of metal nanoparticles take place to reunite and can not be attached on the CNT.CNT produces-COOH through the oxidation processes rear surface,-C=O, groups such as-OH become the nuclearing centre position of metal, but reduction reaction that can not catalytic metal ion, belong to deposition in carbon nano tube surface and GOLD FROM PLATING SOLUTION and carry out, thereby metal can not be realized orientated deposition (Ang L.M., et al with identical speed, Chem.Mater1999,11:2115).Self-assembling method is that functionalized carbon nano tube surface combines with metal ion by complexing, then by electronation obtain metal (Giordano R., Eur.J.Inorg.Chem.2003:610); Or the anchor cooperation of metal nanoparticle by coupling molecule is with directly being assembled in functionalized carbon nano tube surface, this method is mainly used in carbon nano tube surface and coats Au, noble metals such as Rh (Jiang K.Y., et al, Nano Lett.2003,3:275).These class methods can realize the self assembly of nano-metal particle in carbon nano tube surface, but method is loaded down with trivial details, reaction condition is required relatively stricter, the cost height, and load factor is lower, particularly between CNT and the noble metal nano particles if use the coupling molecule contain sulphur atom to produce poisoning effect to catalytic reaction, thereby these class methods are very limited in the prospect that is applied to aspect the Preparation of catalysts.
Summary of the invention
The purpose of this invention is to provide a kind of new method at the directed chemical plated metal nano platinum particle of carbon nano tube surface, can avoid metallic particles self to reunite thus, realize carbon nano tube surface high density loaded metal platinum nano-particle, and be expected to be applied to field such as fuel cell as high activated catalyst.
Technical scheme provided by the invention is: by containing 0.1～10 gram CNT, 1～100 gram surfactant, 0.05～10 gram platinum (in the platinum containing amount in the slaine) in per 1 liter polyalcohol mixed liquor, CNT is mixed by ultrasonic being uniformly dispersed in polyalcohol with the chloride and the surfactant of platinum, under strong agitation, mixed liquor is heated to 120-180 ℃ then, react after 1～2 hour the product centrifugation, washing, vacuum drying then.
CNT is multi-walled carbon nano-tubes or SWCN, carries out earlier surface oxidation treatment before the reaction in strong acid solution.
Surfactant is a quaternary surfactant, ionic liquid surfactant or anionic surfactant, said quaternary surfactant is a DTAB, softex kw or cetyl trimethyl ammonium perchlorate: said ionic liquid surfactant is 1-butyl-3-methylimidazole tetrafluoride boron, 1-ethyl-3-methylimidazole tetrafluoride boron, 1-butyl-3-methylimidazole phosphorus hexafluoride or 1-ethyl-3-methylimidazole phosphorus hexafluoride; Said anionic surfactant is a neopelex, dodecyl sodium sulfate, lauryl sodium sulfate or trifluoromethayl sulfonic acid sodium; The mixture of one or both in the above-mentioned surfactant of reaction employing.
The chloride of platinum is a chloroplatinic acid, potassium chloroplatinate, platinic sodium chloride, platinum tetrachloride or platinous chloride; Said polyalcohol is an ethylene glycol.
Advantage of the present invention is to realize that nano platinum particle in the directed chemical deposition of carbon nano tube surface, has solved metallic particles this technical barrier takes place self to reunite; Realized higher platinum load factor, and be evenly distributed; Can obtain fine and close nano platinum particle layer down in higher load factor (more than 50%), its particle size average out to 5nm, and Size Distribution is very narrow; Product can be used for eelctro-catalyst and other catalytic field of fuel cell.The catalyst prepared with the CNT after the present invention's modification has excellent performance for the methanol oxidation electrocatalytic reaction, obviously is better than similar commercialization catalyst E-TEK.
Description of drawings
The transmission electron microscope photo of the SWCN supported platinum nano particle product (load factor is 50%) that Fig. 1 makes for embodiment 1.
Fig. 2 is the constituent analysis result (EDS) of embodiment 1 product.
Fig. 3 is the result (XPS) of the photoelectron spectroscopy of platinum in embodiment 1 product.
Fig. 4 is that 50%Pt/SWNT catalyst with the preparation of the product of embodiment 1 is to the anodised catalytic performance cyclic voltammetry curve of methyl alcohol figure.
The specific embodiment
Embodiment 1:1) surface oxidation treatment of nanotube: the 1 gram SWCN (Chinese Academy of Sciences's metal provides) or the multi-walled carbon nano-tubes (department of chemistry of Xiamen University provides) of purifying are joined in the round-bottomed flask, add 200 milliliters in 2.6M nitric acid again, heating is boiled, refluxed about 4 hours, filter then, be washed to neutrality, 150 ℃ of dryings 2 hours, the CNT sample that obtains surface oxidation is standby.
2) nano tube supported nano platinum particle: in round-bottomed flask, add CNT 0.1 gram, DTAB 0.1 gram, chloroplatinic acid 0.1 gram and 1000ml ethylene glycol after surface oxidation treatment, place oil bath to add thermal agitation round-bottomed flask after the ultrasonic dispersion, react stop after 2 hours the reaction.
3) with after product centrifugation, the ethanol washing 3 times,, obtain end product 100 ℃ of following vacuum drying.Its nano platinum particle load factor is 50%.
From the visible dense nano platinum particle layer of the transmission electron microscope photo of Fig. 1 product, its particle size average out to 5nm; The constituent analysis result (EDS) of product is as can be known at the content of surperficial platinum quite high (signal of copper comes from copper mesh among the figure) among Fig. 2; Fig. 3 is the result (XPS) of the photoelectron spectroscopy of platinum in the product, by the result as can be known SWCN supported platinum nano particle valence state be zero.
With load the made of carbon nanotubes of nano platinum particle become the catalyst of 50%Pt/SWNT to carry out the anodised catalytic reaction of methyl alcohol.The electrode preparation method of this experiment and experiment condition are according to document (Prabhuram J., J.Phys.Chem.B2003,107:11057) carry out, the platinum load capacity of bibliographical information is that the methanol oxidation peak current density (with respect to true area) of 20% commercialization catalyst E-TEK is lower than 0.33mA/cm
2(obtaining) according to result's reckoning in the literary composition, and the 50%Pt/SWNT of the present invention's preparation is used as catalyst, methanol oxidation peak current density is higher than 1.0mA/cm
2, E-TEK is high more than 3 times for this current value ratio commercialization catalyst, shows to adopt the carbon nanotube loaded nano platinum particle catalyst of the present invention's preparation to have very high catalytic activity (see figure 4).
Embodiment 2～8
The method of nano tube supported nano platinum particle is with embodiment 1, all the other conditions and the results are shown in Table 1:
Table 1
| Embodiment | CNT A | Surfactant B | Platinum salt C | Temperature (℃) | During reaction time H) | Ethylene glycol | Platinum load factor (%) | Platinum grain average-size (nm) | |||
| Kind | Content (gram) | Kind | Content (gram) | Kind | Content (gram) | ||||||
| 1 | A1 | 0.1 | B1 | 0.1 | C1 | 0.1 | 170 | 2 | 1000mL | 50 | 5 |
| 2 | A1 | 10 | | 5 | C2 | 2.5 | 130 | 1.5 | 1000mL | 20 | 3 |
| 3 | A1 | 9 | B5 | 10 | C1 | 1 | 150 | 1. | | 10 | 2.5 |
| 4 | A1 | 10 | B6 | 8 | | 10 | 150 | 2 | 1000mL | 50 | 5.5 |
| 5 | A1 | 4.5 | B9 | 3 | C3 | 0.5 | 160 | 2 | | 10 | 2.5 |
| 6 | A1 | 0.1 | B10 | 0.1 | C4 | 0.01 | 150 | 1 | 1000mL | 9 | 2.8 |
| 7 | A2 | 0.4 | B3 | 0.2 | C5 | 0.4 | 140 | 2 | 1000mL | 50 | 5 |
| 8 | A2 | 0.9 | B4 | 1.2 | C2 | 0.1 | 150 | 1 | | 10 | 2.4 |
| 9 | A2 | 5.7 | B7 | 4 | C1 | 0.3 | 170 | 1 | | 5 | 2 |
| 10 | A2 | 2 | B8 | 2 | C2 | 3 | 130 | 2 | 1000mL | 60 | 6 |
| 11 | A2 | 8 | B11 | 6 | C1 | 2 | 150 | 2 | 1000mL | 20 | 3 |
| 12 | A2 | 0.15 | B 12 | 0.2 | C4 | 0.051 | 150 | 1 | 1000mL | 25 | 4 |
Annotate: A:A1-SWCN, A2-multi-walled carbon nano-tubes
The B:B1-DTAB, the B2-softex kw, B3-cetyl trimethyl ammonium perchlorate, B4-tetrabutylammonium perchlorate, B5-1-butyl-3-methylimidazole tetrafluoride boron, B6-1-ethyl-3-methylimidazole tetrafluoride boron, B7-1-butyl-3-methylimidazole phosphorus hexafluoride, B8-1-ethyl-3-methylimidazole phosphorus hexafluoride, the B9-neopelex, the B10-dodecyl sodium sulfate, B11-lauryl sodium sulfate, B12-trifluoromethayl sulfonic acid sodium
The C:C1-chloroplatinic acid, C2-potassium chloroplatinate, C3-platinic sodium chloride, C4-platinum tetrachloride, C5-platinous chloride
Claims (7)
1. method that is deposited on carbon nano tube surface high density loaded metal platinum by directed chemistry, it is characterized in that by containing 0.1～10 gram CNT in per 1 liter polyalcohol mixed liquor, 1～100 gram surfactant, 0.05～10 gram platinum, CNT is mixed by ultrasonic being uniformly dispersed in polyalcohol with the chloride and the surfactant of platinum, wherein the content of platinum is in the platinum containing amount in the chloride of platinum, mixed liquor is heated to 120～180 ℃ then, react after 1～2 hour the product centrifugation, washing, vacuum drying: said surfactant is a quaternary surfactant, ionic liquid surfactant or anionic surfactant, a kind of surfactant or two kinds of surfactant mixtures are adopted in reaction.
2. as claimed in claim 1ly a kind ofly be deposited on the method for carbon nano tube surface high density loaded metal platinum, it is characterized in that said CNT is multi-walled carbon nano-tubes or SWCN by directed chemistry.
3. as claimed in claim 1ly a kind ofly be deposited on the method for carbon nano tube surface high density loaded metal platinum, it is characterized in that CNT carries out surface oxidation treatment in advance by directed chemistry.
4. as claimed in claim 3ly a kind ofly be deposited on the method for carbon nano tube surface high density loaded metal platinum, it is characterized in that CNT carries out surface oxidation treatment in strong acid solution by directed chemistry.
5. a kind of method that is deposited on carbon nano tube surface high density loaded metal platinum by directed chemistry as claimed in claim 1, it is characterized in that said quaternary surfactant is selected from DTAB, softex kw, a kind of in the cetyl trimethyl ammonium perchlorate; Said ionic liquid surfactant is selected from 1-butyl-3-methylimidazole tetrafluoride boron, 1-ethyl-3-methylimidazole tetrafluoride boron, 1-butyl-3-methylimidazole phosphorus hexafluoride, 1-ethyl-3-methylimidazole phosphorus hexafluoride: said anionic surfactant is selected from neopelex, dodecyl sodium sulfate, lauryl sodium sulfate, trifluoromethayl sulfonic acid sodium.
6. as claimed in claim 1ly a kind ofly be deposited on the method for carbon nano tube surface high density loaded metal platinum by directed chemistry, the chloride that it is characterized in that platinum is chloroplatinic acid, potassium chloroplatinate, platinic sodium chloride, platinum tetrachloride or platinous chloride.
7. as claimed in claim 1ly a kind ofly be deposited on the method for carbon nano tube surface high density loaded metal platinum, it is characterized in that said polyalcohol is an ethylene glycol by directed chemistry.
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| CN100336596C (en) * | 2005-04-08 | 2007-09-12 | 浙江大学 | Preparation method for loading platinum nanoparticles on carbon carrier |
| CN100434167C (en) * | 2005-11-17 | 2008-11-19 | 上海交通大学 | Method for preparing carbon nanometer material carried with noble metal(S) |
| CN100443402C (en) * | 2006-01-26 | 2008-12-17 | 上海交通大学 | Chemical shearing method for preparing high dispersion short carbon nanometer tube |
| CN100428989C (en) * | 2006-09-06 | 2008-10-29 | 大连理工大学 | Method for preparing loading type nano Pd/C catalyst from colloidal solution |
| CN101745433B (en) * | 2008-12-02 | 2013-01-09 | 上海焦化有限公司 | glycol as catalyst prepared by hydrogenising oxalate as well as forming method and application thereof |
| CN102039121B (en) * | 2009-10-21 | 2013-06-05 | 中国科学院大连化学物理研究所 | Platinum/carbon nanotube catalyst and preparation method and application thereof |
| CN102206162B (en) * | 2011-04-06 | 2012-07-18 | 北京理工大学 | Energy-containing oxidant and preparation method thereof |
| CN102219701B (en) * | 2011-04-18 | 2012-07-18 | 北京理工大学 | Energetic salt and preparation method thereof |
| CN102554244B (en) * | 2012-03-12 | 2014-04-09 | 苏州大学 | Self-assembly controllable preparation method of composite of metal nano particles and carbon materials |
| CN103551142A (en) * | 2013-11-04 | 2014-02-05 | 昆明贵研催化剂有限责任公司 | Preparation method of Pt-C (platinum-carbon) catalyst for nitrobenzene hydrogenation |
| CN103954662B (en) * | 2014-03-25 | 2016-06-15 | 西北师范大学 | The preparation of the SDS functionalized carbon nano-tube modified electrode of depositing platinum nanoparticles and to H2O2Detection method |
| CN106111191A (en) * | 2016-06-29 | 2016-11-16 | 兖矿水煤浆气化及煤化工国家工程研究中心有限公司 | A kind of carbon nanotube loaded rhodium catalytic system and application thereof |
| CN114931938B (en) * | 2022-06-15 | 2023-04-07 | 南京工业大学 | Method for preparing cyclopentanol through catalytic hydrogenation of cyclopentanone by using carbon nanotube outer wall loaded platinum nanoparticle catalyst |
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