CN100484631C - Preparation method of catalyst with metal nanoparticles loaded on carbon nano hollow balls - Google Patents
Preparation method of catalyst with metal nanoparticles loaded on carbon nano hollow balls Download PDFInfo
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- CN100484631C CN100484631C CNB2005100401991A CN200510040199A CN100484631C CN 100484631 C CN100484631 C CN 100484631C CN B2005100401991 A CNB2005100401991 A CN B2005100401991A CN 200510040199 A CN200510040199 A CN 200510040199A CN 100484631 C CN100484631 C CN 100484631C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 33
- 239000002077 nanosphere Substances 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920001661 Chitosan Polymers 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 11
- 239000006229 carbon black Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 46
- 241000143432 Daldinia concentrica Species 0.000 claims description 31
- 229910052697 platinum Inorganic materials 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- -1 cation salt Chemical class 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 235000019394 potassium persulphate Nutrition 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 230000008030 elimination Effects 0.000 claims description 4
- 238000003379 elimination reaction Methods 0.000 claims description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000000850 deacetylating effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 abstract 1
- 150000001408 amides Chemical class 0.000 abstract 1
- 125000003277 amino group Chemical group 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 229960000587 glutaral Drugs 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 239000000693 micelle Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 230000005588 protonation Effects 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000002105 nanoparticle Substances 0.000 description 12
- 239000011805 ball Substances 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
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- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
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- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
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Abstract
The present invention relates to a method for preparing catalysts with metal nanoparticles loaded by hollow carbon nanospheres. The method is composed of the following three steps: (1) the preparationThe preparation method for nano carbon hollow carried nano metal particle catalyst comprises three steps: (1) first prepare chitosan nano hollow: add chitosan into omega-olefine acid solution, mix at of chitosan hollow nanospheres: chitosan is added into water solution containing omega-enoic acid, agitation and dissolution are carried out at room temperature so as to filter off insoluble substancroom temperature, filter and obtain micelle-form polymer solution; use potassium persulfate to initiate polymerization reaction of ethenyl, add 25% glutaral liquid to exchange the non-protonation amides and obtain micelle polymer solution, the polyreaction of vinyl is initiated by using potassium persulfate in the filtered solution, amino groups which are unprotonated on the surface are cross-linko on surface and form product; (2) use metal ion salt to absorb on the hollow; (3) put the dried solid into tube furnace, on the protection of nitrogen or reduced hydrogen, heat to 600-850Deg and keeped after 25% of glutaraldehyde water solution is added, and hollow nanospheres of the chitosan are formed; (2) the adsorption of metal ionic salt onto the hollow nanospheres of the chitosan; (3) solid 0.5-4h, then cool to room temperature and obtain carbon black power. This invention is fast, low cost, simple and controllable. s which are dried are put into a tubular furnace, temperature rises to 600 to 800 DEG C under the protection of nitrogen or reducible hydrogen, the temperature then drops to room temperature after maintained for 0.5 to 4 hours, and powder in carbon black is obtained. The method of the present invention has the advantages of low cost, high speed, simplicity, and capability of controlling the preparation of catalysts with metal nanoparticles loaded by hollow carbon nanospheres.
Description
Technical field
The present invention relates to a kind of method for preparing the hollow Nano carbon balls of catalyst with metal nanoparticles loaded with natural chitosan derivatives hollow nano-sphere, prepared catalyst can be directly used in the cathode and anode material of low temperature proton membrane fuel battery (comprising DMFC), belongs to material science and energy science field.
Background technology
Exploitation for free of contamination low temperature proton membrane fuel battery cathode and anode catalyst is the hot research problem of energy science and material science at present.As low temperature proton membrane fuel battery catalyst, metal platinum is occupied important status.In order to increase the specific area of catalyst, the preparation of nano platinum particle is put into research contents, yet, assemble easily because nano level platinum particles surface energy is higher, cause the reduction of catalytic activity and utilization rate.Again because of the price of metal platinum costliness, make that to use the simple metal platinum cell catalyst that acts as a fuel unrealistic.Therefore, people turn to the emphasis of research the research of carbon load platinum catalyst.Material with carbon element is a kind of good conductor on the one hand, can effectively transmit electronics; On the other hand, the loose structure of carbon can fine dispersed catalyst and is improved activity of such catalysts and utilization rate.Therefore, become the research emphasis of fuel battery anode catalyst preparation as the support materials of metallic catalyst nano particle with porous carbon.Although there is several different methods to prepare the catalyst with metal nanoparticles of carbon load at present, as ion-exchange, colloid, chemical vapour deposition (CVD) and electrochemical method, load comprises carbon black, active carbon, carbon nano-fiber, how empty carbon and CNT etc.But these methods generally all need special equipment, complicated preparation method, harsh preparation condition is as high temperature, high pressure etc., the cost height, and the high degree of dispersion of the particle shape of the metal-C catalyst that generates, electrochemical properties, tenor, metal nanoparticle is difficult to control; Therefore, literature method both had been not suitable for breadboard operation, had greatly limited the large-scale production of such catalyst and application widely again.
Summary of the invention
The present invention seeks to propose a kind of low cost, quick, simple, the controlled method for preparing the hollow Nano carbon balls catalyst with metal nanoparticles loaded.
The preparation method of this hollow Nano carbon balls catalyst with metal nanoparticles loaded comprises the steps:
A kind of preparation method of catalyst with metal nanoparticles loaded on carbon nano hollow balls is characterized in that this preparation method is made up of following three steps: (1) is the preparation of preparation shitosan hollow nano-sphere earlier; The preparation of shitosan hollow nano-sphere: shitosan is added in the aqueous solution of ω-olefin(e) acid, stirring at room, dissolving, the elimination insoluble matter, obtain micella sample polymer solution, filtrate is caused the polymerisation of vinyl with potassium peroxydisulfate, adds 25% glutaraldehyde water solution again and the unprotonated amino in surface is carried out crosslinked, forms the shitosan hollow nano-sphere; (2) adsorb on the shitosan hollow nano-sphere with metal cation salt; The shitosan hollow nano-sphere is placed the metal ion saline solution, stirred 1-10 hour, room temperature leaves standstill the back and filters, and repeatedly washs with distilled water, gets solid after the drying.(3) preparation of catalyst with metal nanoparticles loaded on carbon nano hollow balls; the solid of drying is placed tube furnace; logical nitrogen protection or contain under the hydrogen of reproducibility; be warming up to 600-850 ℃; after keeping 0.5-4 hour under this temperature, be cooled to room temperature; obtain carbon black sample powder, be the hollow Nano carbon balls catalyst with metal nanoparticles loaded.
With noble metal platinum, palladium etc. is example, the preparation of (1) shitosan hollow nano-sphere: ω-olefin(e) acid is an acrylic acid, shitosan is added in acrylic acid aqueous solution, and stirring at room, dissolving, the elimination insoluble matter obtains micella sample polymer solution.Filtrate is caused the polymerisation of vinyl with potassium peroxydisulfate, adds 25% glutaraldehyde water solution again and the unprotonated amino in surface is carried out crosslinked, forms the shitosan hollow nano-sphere.
(2) absorption of metal cation salt: the shitosan hollow nano-sphere is placed certain density chloroplatinic acid or palladium nitrate aqueous solution, and electromagnetic agitation 5 hours is filtered after the room temperature standing over night, repeatedly washs with distilled water, gets the glassy yellow solid after the drying.
(3) preparation of hollow Nano carbon balls catalyst with metal nanoparticles loaded: the glassy yellow solid of drying is placed homemade tube furnace; the logical nitrogen protection hydrogen of reproducibility (or contain); speed with 5K/min is warming up to 750 ℃; after keeping 1 hour under this temperature, be cooled to room temperature; obtain carbon black sample powder, be hollow Nano carbon balls loaded metal platinum nano-particle catalyst.
As shown from the above technical solution, the Nano carbon balls in the hollow Nano carbon balls catalyst with metal nanoparticles loaded of the present invention is to utilize wide material sources and free of contamination chitosan derivatives through thermal decomposition carbonization gained; Raw material sources are extensive, cheap, pollution-free; Know that from preparation method this technology is without any need for template and any specialized apparatus of complexity, making step is simple, and any laboratory can large-scale production; From products therefrom, the hollow Nano carbon particle all has complete chondritic, and particle diameter is evenly distributed, and particle diameter can be at 30-100nm, and the metal platinum nano-particle high degree of dispersion and the particle diameter that are carried on the hollow Nano carbon balls are even, can be controlled in 1-50nm; Electro-chemical test shows that it has good catalytic activity to methanol oxidation, so the Nano carbon balls preparation method of this loaded metal platinum nano-particle very easily is used more widely.Use different slaines or multiple metal salt mixture can obtain the Nano carbon balls catalyst of other metal nanoparticle or alloy nano particle load.
Description of drawings
Fig. 1 is a hollow Nano carbon balls loaded metal platinum nano-particle Preparation of catalysts process schematic diagram of the present invention.
Fig. 2 is the structural representation of hollow Nano carbon balls loaded metal platinum nano-particle catalyst of the present invention.
Fig. 3 is the transmission electron microscope photo (100,000 times of multiplication factors) that has adsorbed the anionic shitosan hollow nano-sphere of chloroplatinic acid.
Fig. 4 is the transmission electron microscope photo (80,000 times of multiplication factors) of Nano carbon balls of the supported platinum nano particle of embodiment gained.
Fig. 5 is the high-resolution-ration transmission electric-lens photo of nano platinum particle of the single load of embodiment gained.
Fig. 6 is modified at behind the glass-carbon electrode cyclic voltammetry curve to methyl alcohol catalysis for the hollow Nano carbon balls loaded metal platinum nano-particle catalyst of embodiment gained.Dotted line is not have methyl alcohol in the solution; Solid line is by containing 0.5M methyl alcohol in the solution.Sweep speed is 50mV/s.
The specific embodiment
As shown in Figures 1 and 2, the preparation method of preparation hollow Nano carbon balls catalyst with metal nanoparticles loaded provided by the invention mainly comprises following three steps composition: the preparation of (1) shitosan hollow nano-sphere; (2) absorption of metal cation salt on the shitosan hollow nano-sphere; (3) preparation of hollow Nano carbon balls catalyst with metal nanoparticles loaded.
The preparation method who makes the hollow Nano carbon balls catalyst with metal nanoparticles loaded is that example is illustrated with acrylic acid participation preparation hollow Nano carbon balls catalyst with metal nanoparticles loaded.
The preparation method of hollow Nano carbon balls catalyst with metal nanoparticles loaded is an example with the hollow Nano carbon balls of supported platinum nano particle, can carry out as follows:
(1) preparation of shitosan hollow nano-sphere: shitosan (a) is added in the aqueous solution of acrylic acid (b), the ratio of shitosan/ω-olefin(e) acid amount of substance is 1:1～1:2, and optimal proportion is 1:1.1.Shitosan/ω-the concentration of olefin(e) acid compound in solution is 0.5gL
-1～20gL
-1As 13gL
-1, be lower than or surpass form and the character that this concentration range all can influence product.Stirring at room, dissolving, the elimination insoluble matter obtains micella sample polymer (c) solution.Filtrate is caused the polymerisations of vinyl at 80 ℃ with potassium peroxydisulfate, reaction 2h, be cooled to room temperature after, add 25% glutaraldehyde water solution again and the unprotonated amino in surface carried out crosslinked, form shitosan hollow nano-sphere (d).
Described ω-olefin(e) acid, molecular formula are CH
2=CH-(CH
2) m-COOH, m=0 wherein, 1,2,3,4,5, the shitosan hollow nano-sphere particle diameter minimum that when m is 0, obtains.The chitosan molecule formula is as follows:
Deacetylation is 90～100%, and molecular weight is 25,000～200,000D.
(2) the anionic absorption of chloroplatinic acid: the shitosan hollow nano-sphere is placed certain density chloroplatinic acid aqueous solution, chloroplatinic acid concentration is 0～100mg/mL, and electromagnetic agitation 5 hours is filtered after the room temperature standing over night, repeatedly wash with distilled water, get glassy yellow solid (e) after the drying.Metal cation salt can be chloroplatinic acid, gold chloride, ruthenium trichloride, palladium nitrate etc., adopt the metal ion salt solution of variable concentrations or the chloroplatinic acid/ruthenium trichloride aqueous solution of different proportion, can prepare the metal nanoparticles loaded hollow Nano carbon balls of different metal content or contain the hollow Nano carbon balls of the load platinum ruthenium nanometer particle of different platinum/ruthenium ratio.
The hollow Nano carbon balls average grain diameter is about 30-100nm, and the nano platinum particle high degree of dispersion is in carbon ball surface and carbon ball layer, and average grain diameter is 1-50nm, and the content of metal nanoparticle is 0～36% (w/w).
(3) preparation of the carbon hollow nanospheres of supported platinum nano particle: the glassy yellow solid of drying is placed homemade tube furnace; logical nitrogen (or containing reductive hydrogen) protection; speed with 5K/min is warming up to 750 ℃; after keeping 1 hour, this temperature is cooled to room temperature; get carbon black sample powder, be hollow Nano carbon balls catalyst with metal nanoparticles loaded (f).Logical nitrogen protection, or utilize the nitrogen atmosphere high temperature reduction will obtain same result.
The carbon hollow nanospheres average grain diameter is about 30-100nm; Metal nanoparticle is dispersed in carbon ball surface and the hollow carbon sphere layer, and particle size dispersion is good, can be controlled in 1～50nm, and tenor is 0～36% (w/w).By to the shitosan hollow nano-sphere of adsorbing metal ions in nitrogen atmosphere, pyrolytic or get by the hydrogen high temperature reduction.
The hollow ball shape structure that the anionic chitosan nano ball of transmission electron microscope observing absorption chloroplatinic acid is a regular shape, the shell average-size is about 50nm, boring nuclear is of a size of about 30nm.Nano carbon balls through the thermal decomposition carbonization is the spherical structure of rule under transmission electron microscope, and average grain diameter is about 50nm, and there is ferrous metal particle spot on the surface, and this metallic spot average-size is about 5nm.
The electrochemical properties of hollow Nano carbon balls loaded metal platinum nano-particle catalyst is measured: get the ultrasonic dispersion of Nafion solution of this carbon ball of 1mg and 10 μ l1%, get 2 μ l mixtures and drip and be coated on the glass-carbon electrode of surface finish, dry.With the modified glassy carbon is working electrode, and reversible hydrogen electrode is a reference electrode, and platinum electrode is to electrode, at 0.5MH
2SO
4In the sulfuric acid solution, repeatedly scanning cleaning electrode surface in 0.05～1.2V potential range is again in 0.5MH
2SO
4Among/0.5M the MeOH, in 0.05～1.2V potential range, measure cyclic voltammetry curve.The result shows, load the hollow Nano carbon balls of nano platinum particle methanol oxidation is had good catalytic action, and under experiment condition, show stable catalytic capability.
Claims (5)
1, a kind of preparation method of catalyst with metal nanoparticles loaded on carbon nano hollow balls, it is characterized in that this preparation method is made up of following three steps: (1) is preparation shitosan hollow nano-sphere earlier: shitosan is added in the aqueous solution of ω-olefin(e) acid, stirring at room, dissolving, the elimination insoluble matter, obtain micella sample polymer solution, filtrate is caused the polymerisation of vinyl with potassium peroxydisulfate, add 25% glutaraldehyde water solution again and the unprotonated amino in surface is carried out crosslinked, form the shitosan hollow nano-sphere; (2) adsorb on the shitosan hollow nano-sphere with metal cation salt: the shitosan hollow nano-sphere is placed the metal ion saline solution, stirred 1-10 hour, room temperature leaves standstill the back and filters, and repeatedly washs with distilled water, gets solid after the drying; (3) preparation of catalyst with metal nanoparticles loaded on carbon nano hollow balls, the described solid of drying is placed tube furnace, logical nitrogen protection or contain under the hydrogen of reproducibility, be warming up to 600-850 ℃, after keeping 0.5-4 hour under this temperature, be cooled to room temperature, obtain carbon black sample powder, be catalyst with metal nanoparticles loaded on carbon nano hollow balls; Wherein the ratio of shitosan/ω-olefin(e) acid amount of substance is 1:1～1:2, and the shitosan/ω-concentration of olefin(e) acid compound in solution is 0.5g L
-1～20g L
-1
2, the preparation method of catalyst with metal nanoparticles loaded on carbon nano hollow balls according to claim 1, it is characterized in that filtrate is 80 ℃ of polymerisations that cause vinyl with potassium peroxydisulfate, reaction 2h, after being cooled to room temperature, add 25% glutaraldehyde water solution again and the unprotonated amino in surface is carried out crosslinked, form the shitosan hollow nano-sphere.
3, the preparation method of catalyst with metal nanoparticles loaded on carbon nano hollow balls according to claim 1 and 2 is characterized in that described ω-olefin(e) acid, and molecular formula is CH
2=CH-(CH
2) m-COOH, m=0 wherein, 1,2,3,4,5, the shitosan hollow nano-sphere particle diameter minimum that obtains when m is 0: the chitosan molecule formula is as follows:
Deacetylating degree of chitosan is 90～100%, and molecular weight is 25,000～200,000D.
4, according to the preparation method of claim 1 or 3 described catalyst with metal nanoparticles loaded on carbon nano hollow balls; the preparation that it is characterized in that hollow Nano carbon balls is that the solid with drying places tube furnace; speed with 5K/min when logical nitrogen protection or nitrogen atmosphere high temperature reduction is warming up to 750 ℃; kept 1 hour in this temperature; be cooled to room temperature, obtain carbon black sample powder.
5, according to the preparation method of claim 1 or 3 described catalyst with metal nanoparticles loaded on carbon nano hollow balls, it is characterized in that metal cation salt is chloroplatinic acid, gold chloride or ruthenium trichloride, adopt the metal ion salt solution of variable concentrations or the chloroplatinic acid/ruthenium trichloride aqueous solution of different proportion, the metal nanoparticles loaded hollow Nano carbon balls of preparation different metal content or contain the hollow Nano carbon balls of the load platinum ruthenium nanometer particle of different platinum/ruthenium ratio.
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| CN100455507C (en) * | 2006-03-15 | 2009-01-28 | 哈尔滨工业大学 | Carbon hollow ball with ferrocene and ammonium chloride as raw material and its prepn |
| CN1970203B (en) * | 2006-12-11 | 2010-05-19 | 哈尔滨工业大学 | Method for preparing hollow carbon ball with iron filler |
| CN101815563B (en) * | 2007-07-18 | 2013-02-13 | 新加坡南洋理工大学 | Hollow porous microspheres |
| CN102211204B (en) * | 2011-05-06 | 2013-03-27 | 中国科学院化学研究所 | Method for preparing nano-gold |
| CN102891326A (en) * | 2012-10-23 | 2013-01-23 | 南京交通职业技术学院 | Nitrogen-doped hollow carbon ball loaded palladium-based catalyst and preparation method thereof, and alcohol fuel cell applying same |
| CN108531932B (en) * | 2018-04-11 | 2020-02-21 | 河南郑大催化技术研究院有限公司 | Hollow carbon sphere packaged Ru nanoparticle electrolytic water catalyst and preparation method thereof |
| CN110743539B (en) * | 2019-09-29 | 2022-03-25 | 济南大学 | Method for preparing carbon platinum hollow spheres by using haematococcus pluvialis as reduction template agent |
| CN115285972B (en) * | 2022-08-05 | 2023-07-04 | 湖南师范大学 | Porous carbon-loaded metal nano material and preparation method thereof |
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