CN101491777B - Nickelous chloride assisted synthesis method of fuel cell catalyst carrier ordered mesoporous carbon - Google Patents
Nickelous chloride assisted synthesis method of fuel cell catalyst carrier ordered mesoporous carbon Download PDFInfo
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- CN101491777B CN101491777B CN2008102362730A CN200810236273A CN101491777B CN 101491777 B CN101491777 B CN 101491777B CN 2008102362730 A CN2008102362730 A CN 2008102362730A CN 200810236273 A CN200810236273 A CN 200810236273A CN 101491777 B CN101491777 B CN 101491777B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000000446 fuel Substances 0.000 title claims abstract description 12
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 title claims description 12
- 238000001308 synthesis method Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000001338 self-assembly Methods 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- 238000003763 carbonization Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229920001568 phenolic resin Polymers 0.000 claims description 7
- 239000005011 phenolic resin Substances 0.000 claims description 7
- 238000000935 solvent evaporation Methods 0.000 claims description 7
- 238000012719 thermal polymerization Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 23
- 238000002360 preparation method Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000012528 membrane Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000010411 electrocatalyst Substances 0.000 abstract 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 239000002159 nanocrystal Substances 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 53
- 238000003756 stirring Methods 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910002845 Pt–Ni Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000004966 Carbon aerogel Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910018879 Pt—Pd Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001553 co-assembly Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- -1 polyoxyethylene Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Images
Classifications
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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
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Abstract
The invention relates to a method for the nickel chloride-aided synthesis of fuel cell catalyst carrier ordered mesoporous carbon, which belongs to a preparation process of a direct methanol fuel cell catalyst. The method can produce carbon-carried Pt catalyst with excellent performance by adopting in-situ carbon thermal reduction technique and a unique binary metal loading method and is applicable to oxyhydrogen proton exchange membrane fuel cells and direct methanol fuel cells. The method produces a binary electrocatalyst by using a metal chloride as an additive, synthesizing the ordered mesoporous carbon with a modified soft template self-assembly method, forming a metal nanocrystal through carbon thermal reduction, and loading Pt nano particles with a microwave heating glycol reduction method. The catalyst has excellent electrocatalysis performance and substantially increases the catalytic activity and utilization rate of Pt, thereby having enormous application prospect.
Description
Technical field
A kind of preparation method who is used for the catalyst of fuel batter with proton exchange film carrier ordered mesoporous carbon of this invention.The carbon that adopts original position carbon thermal reduction technology and exclusive binary metal carrying method can make excellent performance carries the Pt catalyst series, is used for hydrogen-oxygen proton exchange membrane fuel cell and DMFC.
Technical background
Proton Exchange Membrane Fuel Cells (PEMFC) eelctro-catalyst commonly used is that carbon carries platinum or platinum base alloy.For reducing the consumption of platinum, improve the utilization rate of platinum, two approach are arranged usually: the one, in Pt, add one or more metal promoters and obtain binary or multicomponent catalyst.The 2nd, adopt the carrier of some high-specific surface areas, such as carbon black, carbon aerogels, CNT or ordered mesopore carbon etc.Ordered mesopore carbon has higher porosity, bigger serface, good electron electric conductivity and higher hydrothermal stability, has just in time satisfied the requirement of catalyst carrier, can be used as the carrier of PEMFC eelctro-catalyst and the skeleton of porous gas diffusive electrode.When behind its area load metal nanoparticle (as Pt, Pd), be good electrode material, can prepare catalytic reaction electrode efficiently, be applied to power conversion and transform device.
For ordered mesopore carbon, traditional preparation method mainly comprises hard template replica method and soft template self-assembly method.Hard template method (S.Jun, S.H.Joo, R.Ryoo, et al.Synthesis of new, nanoporous carbon with hexagonallyordered mesostructure.J.Am.Chem.Soc., 2000,122 (43): be in the nanometer space of silica template, to be filled with organic compounds 10712-10713.), the process that after the high-temperature roasting synthetic carbon is discharged from template.Generally will pass through following step: the micellar structure of utilizing the surfactant self assembly to form is the template synthesizing mesoporous monox, and carbon source is filled in the mesopore silicon oxide duct, and polymerization and carbonization are at last with HF or NaOH solution removal silica template.Defective with hard template method is to prepare the silica template in advance, and whole process is more loaded down with trivial details, and cost is higher, is difficult to suitability for industrialized production, thereby its range of application has bigger limitation.And soft template method utilizes surfactant as directed agents, and self assembly forms the structure of high-sequential, and the surfactant decomposition stays hole in the carbonisation, obtains the mesoporous carbon consistent with the surfactant micella structure.(R.L.Liu such as Zhao Dongyuan, Y.F.Shi, Y.Wan, et al.Triconstituent co-assembly to ordered mesostructured polymer-silica and carbon-silica nanocomposites and large-poremesoporous carbons with high surface areas.J.Am.Chem.Soc., 2006,128 (35): 11652-11662.) developed soft template method, with resol resin is polymer precursor, oligomer silicate is inorganic precursor, triblock copolymer F127 is a template, polymer-the silica and the carbon-monox nanometer compound that have prepared high-sequential have greatly been simplified the synthesis step of meso-porous carbon material.But when adopting this ordered mesopore carbon to act as a fuel cell catalyst carrier, carbon particulate can not be distilled water infiltration fully, even also still be difficult to disperse under magnetic agitation or supersonic oscillations, has particulate to be deposited in beaker bottom in the whole process all the time.The hydrophobicity performance of this carbon particulate causes the Pt nano particle obviously to be reunited, even load factor is extremely low, thereby has weakened the electrocatalysis characteristic of Pt nano particle.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of easy ordered mesopore carbon, formed exclusive binary metal carrying method, obtain the used in proton exchange membrane fuel cell catalyst material of high catalytic activity after the supporting Pt.
The present invention comprises following steps: (1), on the basis of soft template self-assembly method surfactant F127, phenolic resins and ethyl orthosilicate are mixed, in adding nickel chloride, palladium bichloride, chromium chloride, iron chloride, the cobalt chloride solution any or several compound, the amount of metallics is 0.1～0.8mmol, and the mass fraction in the mesoporous carbon composite material of metal after roasting is 2%～20%; (2), room temperature solvent evaporation, after 70～120 ℃ of thermal polymerizations, form soft film; (3), carbonisation is connected with the protection of nitrogen or argon stream, heating rate is 1 ℃ of min
-1, promptly get ordered mesopore carbon-silica compound; (4), remove silica, through centrifugation, washing, drying, promptly obtain ordered mesopore carbon with the mixed solution of NaOH, second alcohol and water.
This invention adds metal chloride in the building-up process of soft template self-assembly method, replace hydrochloric acid generation proton and come the hydrolysis ethyl orthosilicate, can prevent caving in of carbon skeleton structure.On the other hand, it is nanocrystalline finally to change metal simple-substance into after the thermal reduction of the slaine of adding process pyrocarbon, has improved the electric conductivity of carbon, has also improved the hydrophily of carbon and has supported performance.And, form Pt base binary catalyst after the supporting Pt, increased the catalytic active site of Pt, can increase substantially the catalytic performance and the effective rate of utilization of catalyst.
Description of drawings
Fig. 1 is the big angle XRD figure of prepared ordered mesopore carbon.
Fig. 2 be the present invention prepared at 0.5molL
-1H
2SO
4Cyclic voltammetry curve in the solution, sweep speed are 20mVs
-1, 25 ℃.(a)Pt/C-Ni(0)，(b)Pt/C-Ni(5)，(c)Pt/C-Ni(10)，(d)Pt/C-Ni(15)，(e)Pt/C-Ni(20)。
Fig. 3 is that the prepared Pt/C-Ni of the present invention (x) catalyst is at 1.0molL
-1H
2SO
4+ 2.0molL
-1CH
3Cyclic voltammetry curve in the OH solution, sweep speed are 20mVs
-1, 25 ℃.
Fig. 4 takes off the peak according to Pt among Fig. 2 to the suction of hydrogen, deducts the influence of electric double layer electric current, has provided the electro-chemical activity area (EAS) of different catalysts, and according to bimodal to oxidization of methanol among Fig. 3, the mass ratio activity that provides (Mass activity).
The specific embodiment
Specific embodiment one:
(1) on the basis of soft template self-assembly method, adds nickel chloride solution.That is: 1.0g surfactant PluronicF127 (polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymer) is dissolved in the 10.0g absolute ethyl alcohol, stirs and form transparent solution.Add 3.0mL, 0.2molL
-1Nickel chloride solution, 40 ℃ continue down to stir 1h.Slowly drip the ethanolic solution (20%) of 2.08g ethyl orthosilicate, 2.5g phenolic resins, stir 2h it is mixed.
(2) mixture is transferred in the flat bottom evaporating dishes,double, solvent evaporation 5～8h puts into 100 ℃ of thermal polymerization 24h of vacuum drying chamber under room temperature (25 ℃), forms soft film.
(3) carbonization is carried out in being connected with the atmosphere tube type stove of stream of nitrogen gas.At 900 ℃ of insulation 2h, heating rate is strict controlled in 1 ℃ of min
-1, promptly get ordered mesopore carbon-silica compound.
(4) use the mixed solution (mass ratio=0.4: 10: 8) of NaOH, second alcohol and water to soak sample 24h after carbonization is ground again, remove silica.
(5) centrifugation is respectively washed 2 times with deionized water and ethanol respectively; Dry in 80 ℃ of baking ovens, promptly obtain ordered mesopore carbon, called after C-Ni (15).
(6) the synthesising mesoporous carbon loaded Pt catalyst of heating using microwave reduction of ethylene glycol method Pt/C-Ni (15), wherein the Theoretical Mass mark of Pt is 20%.
This method is simple, and preparation cost is cheap, and the product of acquisition all has the two-dimentional hexagonal structure of high-sequential, and space group is p6mm, and has obtained the metal simple-substance Ni (see figure 1) of face-centred cubic structure.Adding the preparation-obtained material with carbon element of 15% nickel chloride in the preparation process is the BET specific area maximum of C-Ni (15), reaches 1220.2m
2G
-1, total pore volume reaches 1.13cm
3G
-1, size distribution is narrow, concentrates on 5.1nm.Become the Pt-Ni binary catalyst after the heated by microwave reduction of ethylene glycol method supporting Pt, Pt/C-Ni (15) electrocatalysis characteristic excellence reaches 78.5m to the electro-chemical activity area of absorption hydrogen
2G
-1, the mass ratio activity of methyl alcohol is reached 244.5mAmg
-1Pt is 3-14 times when not adding nickel chloride, has great application prospect.
Specific embodiment two (comparative example):
(1) 1.0g surfactant F127 is dissolved in the 10.0g absolute ethyl alcohol, stirs and form transparent solution.Do not add nickel chloride solution, 40 ℃ continue to stir 1h down.Slowly drip the ethanolic solution (20%) of 2.08g ethyl orthosilicate, 2.5g phenolic resins, stir 2h it is mixed.
(2) mixture is transferred in the flat bottom evaporating dishes,double, solvent evaporation 5～8h puts into 100 ℃ of thermal polymerization 24h of vacuum drying chamber under room temperature (25 ℃), forms soft film.
(3) carbonization is carried out in being connected with the atmosphere tube type stove of stream of nitrogen gas.At 900 ℃ of insulation 2h, heating rate is strict controlled in 1 ℃ of min
-1, promptly get ordered mesopore carbon-silica compound.
(4) (mass ratio=0.4:10:8) soaks the sample 24h after carbonization is ground, and removes silica to use the mixed solution of NaOH, second alcohol and water again.
(5) centrifugation is respectively washed 2 times with deionized water and ethanol respectively; Dry in 80 ℃ of baking ovens, promptly obtain ordered mesopore carbon, called after C-Ni (0).
(6) the synthesising mesoporous carbon loaded Pt catalyst of heating using microwave reduction of ethylene glycol method Pt/C-Ni (0), wherein the Theoretical Mass mark of Pt is 20%.
The material with carbon element that does not add nickel chloride in the preparation process is that the BET specific area of C-Ni (O) is 745.9m
2G
-1, total pore volume reaches 0.66cm
3G
-1, size distribution is narrow, concentrates on 3.6nm.By cyclic voltammetry experiment test, in Ni content 0～20% series, the electrocatalysis characteristic of Pt/C-Ni (O) is the poorest, to the electro-chemical activity area of absorption hydrogen 24.9m only
2G
-1, the mass ratio activity of methyl alcohol is had only 17.2mAmg
-1Pt.
Specific embodiment three:
(1) on the basis of soft template self-assembly method, adds nickel chloride solution.That is: 1.0g template agent F127 is dissolved in the 10.0g absolute ethyl alcohol, stirs and form transparent solution.Add 4.0mL, 0.2molL
-1Nickel chloride solution, 40 ℃ continue down to stir 1h.Slowly drip the ethanolic solution (20%) of 2.08g ethyl orthosilicate, 2.5g phenolic resins, stir 2h it is mixed.
(2) mixture is transferred in the flat bottom evaporating dishes,double, solvent evaporation 5～8h puts into 100 ℃ of thermal polymerization 24h of vacuum drying chamber under room temperature (25 ℃), forms soft film.
(3) carbonization is carried out in being connected with the atmosphere tube type stove of stream of nitrogen gas.At 900 ℃ of insulation 2h, heating rate is strict controlled in 1 ℃ of min
-1, promptly get ordered mesopore carbon-silica compound.
(4) (mass ratio=0.4:10:8) soaks the sample 24h after carbonization is ground, and removes silica to use the mixed solution of NaOH, second alcohol and water again.
(5) centrifugation is respectively washed 2 times with deionized water and ethanol respectively; Dry in 80 ℃ of baking ovens, promptly obtain ordered mesopore carbon, called after C-Ni (20).
(6) the synthesising mesoporous carbon loaded Pt catalyst of heating using microwave reduction of ethylene glycol method Pt/C-Ni (20), wherein the Theoretical Mass mark of Pt is 20%.
Material with carbon element of the present invention is that the BET specific area of C-Ni (20) is 776.3m
2G
-1, total pore volume 0.98cm
3G
-1, size distribution is narrow, concentrates on 3.7nm.Become the Pt-Ni binary catalyst after the heated by microwave reduction of ethylene glycol method supporting Pt, the electrocatalysis characteristic of Pt/C-Ni (20) is poor than Pt/C-Ni (15), to the electro-chemical activity area 33.5m of absorption hydrogen
2G
-1, to the active 22.7mAmg of the mass ratio of methyl alcohol
-1Pt.May be that specific area has only 60% of C-Ni (15), has reduced the utilization rate of Pt because the structural behaviour of C-Ni (20) is poor.
Specific embodiment four:
(1) on the basis of soft template self-assembly method, adds palladium chloride solution.That is: 1.0g template agent F127 is dissolved in the 10.0g absolute ethyl alcohol, stirs and form transparent solution.Add 2.0mL, 0.2molL
-1Palladium chloride solution, 40 ℃ continue down to stir 1h.Slowly drip the ethanolic solution (20%) of 2.08g ethyl orthosilicate, 2.5g phenolic resins, stir 2h it is mixed.
(2) mixture is transferred in the flat bottom evaporating dishes,double, solvent evaporation 5～8h puts into 100 ℃ of thermal polymerization 24h of vacuum drying chamber under room temperature (25 ℃), forms soft film.
(3) carbonization is carried out in being connected with the atmosphere tube type stove of stream of nitrogen gas.At 900 ℃ of insulation 2h, heating rate is strict controlled in 1 ℃ of min
-1, promptly get ordered mesopore carbon-silica compound.
(4) (mass ratio=0.4:10:8) soaks the sample 24h after carbonization is ground, and removes silica to use the mixed solution of NaOH, second alcohol and water again.
(5) centrifugation is respectively washed 2 times with deionized water and ethanol respectively; Dry in 80 ℃ of baking ovens, promptly obtain ordered mesopore carbon, called after C-Pd (10).
(6) the synthesising mesoporous carbon loaded Pt catalyst of heating using microwave reduction of ethylene glycol method Pt/C-Pd (10), wherein the Theoretical Mass mark of Pt is 20%.
Material with carbon element of the present invention is to become the Pt-Pd binary catalyst after C-Pd (10) supporting Pt, to the electro-chemical activity area of absorption hydrogen up to 166.9m
2G
-1, to the active 260.9mAmg of the mass ratio of methyl alcohol
-1Pt.
Specific embodiment five:
(1) on the basis of soft template self-assembly method, adds ferric chloride solution.That is: 1.0g template agent F127 is dissolved in the 10.0g absolute ethyl alcohol, stirs and form transparent solution.Add 2.0mL, 0.2molL
-1Ferric chloride solution, 40 ℃ continue down to stir 1h.Slowly drip the ethanolic solution (20%) of 2.08g ethyl orthosilicate, 2.5g phenolic resins, stir 2h it is mixed.
(2) mixture is transferred in the flat bottom evaporating dishes,double, solvent evaporation 5～8h puts into 100 ℃ of thermal polymerization 24h of vacuum drying chamber under room temperature (25 ℃), forms soft film.
(3) carbonization is carried out in being connected with the atmosphere tube type stove of stream of nitrogen gas.At 900 ℃ of insulation 2h, heating rate is strict controlled in 1 ℃ of min
-1, promptly get ordered mesopore carbon-silica compound.
(4) (mass ratio=0.4:10:8) soaks the sample 24h after carbonization is ground, and removes silica to use the mixed solution of NaOH, second alcohol and water again.
(5) centrifugation is respectively washed 2 times with deionized water and ethanol respectively; Dry in 80 ℃ of baking ovens, promptly obtain ordered mesopore carbon, called after C-Fe (10).
(6) the synthesising mesoporous carbon loaded Pt catalyst of heating using microwave reduction of ethylene glycol method Pt/C-Fe (10), wherein the Theoretical Mass mark of Pt is 20%.
Material with carbon element of the present invention is to become the Pt-Fe binary catalyst after C-Fe (10) supporting Pt, to the electro-chemical activity area of absorption hydrogen up to 128.0m
2G
-1, to the active 123.9mAmg of the mass ratio of methyl alcohol
-1Pt.
Claims (1)
1. the method for the auxiliary synthetic fuel cell catalyst carrier ordered mesoporous carbon of a chloride is characterized in that comprising following steps:
(1), on the basis of soft template self-assembly method, surfactant polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymer, phenolic resins and ethyl orthosilicate are mixed, in adding nickel chloride, palladium bichloride, chromium chloride, iron chloride, the cobalt chloride solution any or several compound, the mole of above-mentioned metal chloride is 0.1～0.8mmol, and the mass fraction in the mesoporous carbon composite material of metal after roasting is 2%～20%;
(2), room temperature solvent evaporation, after 70～120 ℃ of thermal polymerizations, form soft film;
(3), carbonisation is connected with the protection of nitrogen or argon stream, heating rate is 1 ℃ of min
-1, promptly get ordered mesopore carbon-silica compound;
(4), remove silica, through centrifugation, washing, drying, promptly obtain ordered mesopore carbon with the mixed solution of NaOH, second alcohol and water.
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