CN102247869A - Spherical nitrogen-doped carbon-supported non-noble metal oxygen reduction catalyst and preparation method thereof - Google Patents
Spherical nitrogen-doped carbon-supported non-noble metal oxygen reduction catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a spherical nitrogen-doped carbon-supported non-noble metal oxygen reduction catalyst and a preparation method thereof, and aims to provide a nitrogen-doped non-noble metal oxygen reduction catalyst which has the advantages of simplicity, convenience, practicability, low cost and stable performance and a preparation method thereof. The technical key points are as follows: the catalyst comprises the following components: melamine formaldehyde resin prepolymer, non-noble metal salt and acid. The preparation method of the catalyst comprises the following steps of: (1) uniformly mixing the melamine formaldehyde resin prepolymer with pure water; (2) adding the non-noble metal salt and stirring; (3) adding the acid into the solution obtained by the step (2), curing and drying to obtain blocks; and (4) performing thermal treatment to obtain the spherical nitrogen-doped carbon-supported non-noble metal oxygen reduction catalyst. The invention belongs to the technical field of fuel cell material science.
Description
Technical field
The present invention relates to a kind of oxygen reduction catalyst and preparation method thereof, specifically, is that a kind of spherical nitrogen-doped carbon carries non noble metal oxygen reduction catalyst and preparation method thereof, belongs to the fuel cell material science and technology field.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) has energy density height, advantages of environment protection, is considered to the future transportation instrument, disperses one of main alternative energy source of power station and portable electronic products etc.Because the PEMFC negative electrode is an oxygen electrode, oxygen electrode process invertibity is little, and the reduction difficulty must be used a large amount of noble metal platinum (Pt) catalyst, causes the battery cost too high, has seriously hindered the commercialization of PEMFC.Particularly methanol crossover causes on the negative electrode Pt catalyst taking place the electroxidation of methyl alcohol in DMFC (DMFC), produce " mixed potential ", and the toxicity intermediate that methanol oxidation produces easily makes catalyst poisoning, has a strong impact on the output performance of battery.Therefore developing highly active anti-pure non noble metal oxygen reduction catalyst is one of key issue of present PEMFC and DMFC research.
Jasinski used the nitrogen containing metal macrocyclic compound as oxygen reduction electro-catalyst (Jasinski R. Nature in 1964,1964,201,1212-1213), then numerous scholars have carried out a large amount of research to nitrogenous non noble metal oxygen reduction catalyst, the Ma Zifeng of Shanghai Communications University etc. use carbon material supported metal phthalocyanine, metalloporphyrin is (as tetramethoxy phenyl cobalt porphyrin, tetramethoxy phenyl ferriporphyrin), high-temperature heat treatment in inert atmosphere then, make oxygen reduction catalyst and (appoint lofty ideal with better activity, fiber crops rosy clouds dawn, Xie Xianyu, Yan Tao, Ma Zifeng.The chemical industry journal, 2006,57,2597-2603; Xuanying DENG, Dongyun ZHANG, Xin WANG, Xianxia YUAN, Zifeng MA. Chinese Journal of Catalysis, 2008,29,519-523), Rajesh Bashyam and Piotr Zelenay use carbon to carry polypyrrole load cobalt nitrate, through NaBH
4Electronation make oxygen reduction electro-catalyst (Rajesh Bashyam, Piotr Zelenay. Nature, 2006,443,63-66).F. Jaouen and F. Charreteur etc. are adsorbed on ferric acetate on the carbon carrier, then at NH
3/ H
2900 ℃ of heat treatments in the/Ar mixed atmosphere, make iron-based PEMFC oxygen reduction catalyst (F. Jaouen, F. Charreteur, J. P. Dodelet. Journal of The Electrochemical Society, 2006,153, A689-A698).Ye Siyu etc. is dissolved in N with polyacrylonitrile, and dinethylformamide adds cobalt chloride then, through solgel reaction, CO
2Supercritical drying, make the polyacrylonitrile organic aerogel that contains cobalt, 900 ℃ of high-temperature heat treatment make the carbon aerogels oxygen reduction electro-catalyst (SiyuYe that contains cobalt under inert atmosphere then, Ashok K.Vijh. International Journal of Hydrogen Energy, 2005,30,1011-1015).Chinese patent CN101884932A has announced that a kind of employing electrostatic spinning technique prepares polymer fiber, and high-temperature heat treatment makes nitrogen-doped nanometer fiber oxygen reduction catalyst in nitrogen containing atmosphere.Chinese patent CN101859906A has announced a kind of with cobalt chloride, nitrogenous source (melamine or hexamethylenetetramine), the grinding of carbon black (acetylene black or Vulcan XC-72R) mixing machinery, and high-temperature heat treatment makes non noble metal oxygen reduction catalyst under nitrogen protection.
Above-mentioned method for preparing catalyst is mostly comparatively complicated, expend lot of manpower and material resources, and the preparation process process conditions is wayward, is unfavorable for the catalyst industrialization.Therefore the simple low cost of development process, highly active oxygen reduction electro-catalyst system are significant for the development and the industrialization process that promote Proton Exchange Membrane Fuel Cells.
Summary of the invention
At the problems referred to above, the invention provides a kind of cheap, stable high spherical nitrogen-doped carbon and carry non noble metal oxygen reduction catalyst and preparation method thereof.
First purpose of the present invention is: provide a kind of spherical nitrogen-doped carbon to carry non noble metal oxygen reduction catalyst, this Preparation of Catalyst raw material is following component: melamine resin, base metal salt and acid, wherein, the mass ratio of the carbon of the metallic element of base metal salt and melamine resin is 1 ﹕, 100～25 ﹕ 100.
Described base metal salt is one or more in cobalt nitrate, ferric nitrate, cobalt acetate, the ferric acetate.
Described acid comprises that the one or more combination in glacial acetic acid and hydrochloric acid, nitric acid, the sulfuric acid forms.
The quality percentage composition of described glacial acetic acid is 70～90 % of sour gross mass, and the combination quality percentage composition of one or more in hydrochloric acid, nitric acid, the sulfuric acid accounts for 10～30 % of sour total amount.
Described melamine resin solid content is 60%.
Another object of the present invention is, provides a kind of spherical nitrogen-doped carbon to carry the preparation method of non noble metal oxygen reduction catalyst, in turn includes the following steps:
(1) 10～100 parts melamine resin and 0～10 part pure water are mixed;
(2) add base metal salt again, stir 10～60 min, make base metal salt be dissolved in the melamine resin performed polymer fully, form the liquid of homogeneous;
(3) acid is added in the solution of gained step (2) gained and transfer to pH value 1～4, static 10 min ~ 24 h, after treating to solidify fully, the reduced vacuum drying obtains the melamino-formaldehyde xerogel that bulk contains base metal salt;
(4) the melamino-formaldehyde xerogel that the gained bulk is contained base metal salt heat treatment under 600～900 ℃ of conditions in inert atmosphere promptly obtains spherical nitrogen-doped carbon and carries the non noble metal oxygen reduction eelctro-catalyst.
Above-mentioned a kind of spherical nitrogen-doped carbon carries the preparation method of non noble metal oxygen reduction catalyst, and wherein, described inert gas is: Ar, He or N
2
Above-mentioned a kind of spherical nitrogen-doped carbon carries the preparation method of base metal doped with oxygen reducing catalyst, and wherein, the vacuum of reduced vacuum drying is less than 0.09 MPa, and temperature is 20～50 ℃; Time is 1～3 h.
Above-mentioned a kind of spherical nitrogen-doped carbon carries the preparation method of base metal doped with oxygen reducing catalyst, wherein, and described high-temperature heat treatment times 30～180 min.
Oxygen reduction catalyst provided by the present invention has following advantage:
1, have continuously chondritic uniformly, the BET specific area of catalyst is 250～800 m
2/ g, particle diameter is less than 40 μ m.
2, with the melamine resin and the preparation of base metal salt of high nitrogen content, raw material are easy to get, and are cheap, and preparation process is simple, and it is low effectively to reduce the catalyst cost, and stable catalytic performance is arranged, and can improve the service life of air cell by a relatively large margin.
3, the metal-CN structure in the melamine resin resin carbon aerogels oxygen reduction catalyst is one of major reason that influences catalyst activity, in building-up process, directly transition metal salt is added in the melamine resin, slaine is participated in reaction directly and can be formed more stable metal-CN structure in the solidification process of resin, thereby effectively improves activity of such catalysts.
4, this catalyst is used for electrode material, has higher electric conductivity; Three-electrode system (saturated calomel electrode is a reference electrode, and platinized platinum is to electrode, and the glass-carbon electrode that is coated with diameter 4 mm of catalyst is a working electrode), electrolyte is 0.5 mol/L H
2SO
4Test in the solution, sweep speed and be 50mV/s, the result shows that non noble metal oxygen reduction eelctro-catalyst of the present invention has catalytic activity preferably, and the hydrogen reduction spike potential can reach 0.3 V(vs. SCE).
5, catalyst particularly in DMFC, has been avoided the anodal potential loss that causes in the positive pole reaction from the methyl alcohol that negative pole sees through to also original very high selection of oxygen.
Description of drawings
Fig. 1 is that the prepared spherical nitrogen-doped carbon of the present invention carries the cobalt oxygen reduction electro-catalyst at 0.5 saturated mol/L H of oxygen
2The polarization curve of different rotating speeds in the SO4 solution;
Fig. 2 is that the prepared spherical nitrogen-doped carbon of the present invention carries the DMFC monocell performance map that the cobalt oxygen reduction electro-catalyst is a cathod catalyst;
Fig. 3 carries the cobalt oxygen reduction electro-catalyst at 0.5 saturated mol/L H of oxygen to the prepared spherical nitrogen-doped carbon of the present invention
2SO
4The polarization curve of different rotating speeds in the solution;
Fig. 4 is that the prepared spherical nitrogen-doped carbon of the present invention carries the DMFC monocell performance map that the cobalt oxygen reduction electro-catalyst is a cathod catalyst;
Fig. 5 is that the prepared spherical nitrogen-doped carbon of the present invention carries ferroelectric catalyst at 0.5 saturated mol/L H of oxygen
2SO
4The polarization curve of different rotating speeds in the solution;
Fig. 6 is that the prepared spherical nitrogen-doped carbon of the present invention carries the DMFC monocell performance map that the iron oxygen reduction electro-catalyst is a cathod catalyst;
Fig. 7 is that the prepared spherical nitrogen-doped carbon of the present invention carries the ferro-cobalt oxygen reduction electro-catalyst at 0.5 saturated mol/L H of oxygen
2SO
4The polarization curve of different rotating speeds in the solution;
Fig. 8 is that the prepared spherical nitrogen-doped carbon of the present invention carries the DMFC monocell performance map that the ferro-cobalt oxygen reduction electro-catalyst is a cathod catalyst.
The specific embodiment
The present invention is described in further detail below in conjunction with specific embodiment, but any limitation of the invention that does not constitute.
Embodiment 1
(1) with 40 parts of solid contents 60% of weight portion, the melamine resin performed polymer of pH value 7～9, with weight portion be 10 parts pure water, stir 10 min and mix;
(2) 2 parts of cobalt nitrates of weight portion are added the melamine resin performed polymer that mixes, stir 60 min, make cobalt nitrate be dissolved in the melamine resin performed polymer fully;
(3) glacial acetic acid is added the melamine resin performed polymer that is dissolved with cobalt nitrate, transferring to the pH value is 1.5, leaves standstill 10 min, treats that it solidifies the back fully under 30 ℃, and dry 3 h of reduced vacuum obtain the melamino-formaldehyde xerogel that bulk contains cobalt nitrate;
(4) the melamino-formaldehyde xerogel that bulk is contained cobalt nitrate 700 ℃ of heat treatment 1 h under the Ar protection pulverize after the cooling, and 300 orders sieve, and promptly obtain spherical nitrogen-doped carbon and carry the cobalt oxygen reduction electro-catalyst.
Consult Fig. 1, prepared spherical nitrogen-doped carbon is carried the cobalt oxygen reduction electro-catalyst at 0.5 saturated mol/L H of oxygen
2SO
4The polarization curve of different rotating speeds in the solution; Consult Fig. 2, prepared spherical nitrogen-doped carbon carries the DMFC monocell performance that the cobalt oxygen reduction electro-catalyst is a cathod catalyst, and condition is: at PtRu/C(Johnson Matthey Inc.) as anode catalyst, the PtRu carrying capacity is 4 mg/cm
2, cathod catalyst carries Co catalysts for the self-control nitrogen-doped carbon, and the metal carrying capacity is 10 mg/cm
2, PEM adopts Nafion 117 films (DuPont), forms monocell.The battery operation condition is: methanol concentration 2 mol/L, methyl alcohol flow velocity 1 mL/min, oxygen gas flow rate 100 mL/min, 60 ℃ of temperature.
Embodiment 2
(1) with weight portion be 40 solid content 60%, the melamine resin performed polymer of pH value 7～9 and weight portion are 5 pure water, stir 10min and mix;
(2) 2 parts of cobalt acetates of weight portion are added the melamine resin performed polymer that mixes, stir 30min, make cobalt acetate be dissolved in the melamine resin performed polymer fully;
(3) the molten adding of 10% hydrochloric acid is dissolved with the melamine resin performed polymer of cobalt acetate, transferring to the pH value is 2.0, leaves standstill 30 min, treats that it solidifies the back fully under 30 ℃, dry 3 h of reduced vacuum obtain the melamino-formaldehyde xerogel that bulk contains cobalt acetate;
(4) the melamino-formaldehyde xerogel that bulk is contained cobalt acetate 750 ℃ of heat treatment 1.0 h under the Ar protection pulverize after the cooling, and 300 orders sieve, and promptly obtain spherical nitrogen-doped carbon and carry the cobalt oxygen reduction electro-catalyst.
Consult Fig. 3, prepared spherical nitrogen-doped carbon is carried the cobalt oxygen reduction electro-catalyst at 0.5 saturated mol/L H of oxygen
2SO
4The polarization curve of different rotating speeds in the solution; Consult Fig. 4, prepared spherical nitrogen-doped carbon carries the DMFC monocell performance that the cobalt oxygen reduction electro-catalyst is a cathod catalyst.Condition is with embodiment 1.
Embodiment 3
(1) with the solid content 60% of 50 parts of weight portions, the melamine resin performed polymer of pH value 7～9 and 10 parts pure water stir 10min and mix;
(2) 5 parts of ferric acetates of weight portion are added the melamine resin performed polymer that mixes, stir 30min, make ferric acetate be dissolved in the melamine resin performed polymer fully;
(3) 15% nitric acid is dropwise added the melamine resin performed polymer that is dissolved with ferric acetate, transferring to the pH value is 3.0, leaves standstill 5 h, treats that it solidifies the back fully under 30 ℃, and dry 3 h of reduced vacuum obtain the melamino-formaldehyde xerogel that bulk contains ferric acetate;
(4) bulk is contained the melamino-formaldehyde xerogel of ferric acetate at N
2Protect following 700 ℃ of heat treatment 2 h, pulverize after the cooling, 300 orders sieve, and promptly obtain spherical nitrogen-doped carbon and carry the iron oxygen reduction electro-catalyst.
Consult Fig. 5, prepared spherical nitrogen-doped carbon is carried the iron oxygen reduction electro-catalyst at 0.5 saturated mol/L H of oxygen
2SO
4The polarization curve of different rotating speeds in the solution; Consult Fig. 6, prepared spherical nitrogen-doped carbon carries the DMFC monocell performance that the iron oxygen reduction electro-catalyst is a cathod catalyst.Condition is with embodiment 1.
Embodiment 4
(1) with the solid content 60% of 40 parts of weight portions, the melamine resin performed polymer of pH value 7～9 and 20 parts pure water stir 10min and mix;
(2) 3 parts of cobalt acetates of weight portion and 3 parts of ferric acetates are added the melamine resin performed polymer that mixes, stir 60min, make cobalt acetate and ferric acetate be dissolved in the melamine resin performed polymer fully;
(3) 10% sulfuric acid is dropwise added the melamine resin performed polymer that is dissolved with cobalt acetate and ferric acetate, transferring to the pH value is 3.5, leaves standstill 20 h, treats that it solidifies the back fully under 30 ℃, dry 3 h of reduced vacuum obtain the melamino-formaldehyde xerogel that bulk contains cobalt acetate and ferric acetate;
(5) bulk is contained the melamino-formaldehyde xerogel of cobalt acetate and ferric acetate at N
2Protect following 700 ℃ of heat treatment 2 h, pulverize after the cooling, 300 orders sieve, and promptly obtain spherical nitrogen-doped carbon and carry the ferro-cobalt oxygen reduction electro-catalyst.
Consult Fig. 7, prepared spherical nitrogen-doped carbon is carried the ferro-cobalt oxygen reduction electro-catalyst at 0.5 saturated mol/L H of oxygen
2SO
4The polarization curve of different rotating speeds in the solution; Consult Fig. 8, prepared spherical nitrogen-doped carbon carries the DMFC monocell performance that the ferro-cobalt oxygen reduction electro-catalyst is a cathod catalyst.Condition is with embodiment 1.
Claims (9)
1. a spherical nitrogen-doped carbon carries non noble metal oxygen reduction catalyst, it is characterized in that, this Preparation of Catalyst raw material is following component: melamine resin, base metal salt and acid, wherein, the mass ratio of the carbon of the metallic element of base metal salt and melamine resin is 1 ﹕, 100～25 ﹕ 100.
2. a kind of spherical nitrogen-doped carbon according to claim 1 carries non noble metal oxygen reduction catalyst, it is characterized in that, described base metal salt is one or more in cobalt nitrate, ferric nitrate, cobalt acetate, the ferric acetate.
3. a kind of spherical nitrogen-doped carbon according to claim 1 carries non noble metal oxygen reduction catalyst, it is characterized in that, described acid comprises that the one or more combination in glacial acetic acid and hydrochloric acid, nitric acid, the sulfuric acid forms.
4. a kind of spherical nitrogen-doped carbon according to claim 3 carries non noble metal oxygen reduction catalyst, it is characterized in that, the quality percentage composition of described glacial acetic acid is 70～90 % of sour gross mass, and the combination quality percentage composition of one or more in hydrochloric acid, nitric acid, the sulfuric acid accounts for 10～30 % of sour total amount.
5. a kind of spherical nitrogen-doped carbon according to claim 1 carries non noble metal oxygen reduction catalyst, it is characterized in that, described melamine resin solid content is 60%.
6. a spherical nitrogen-doped carbon carries the preparation method of non noble metal oxygen reduction catalyst, it is characterized in that, in turn includes the following steps:
(1) be that the pure water that 10～100 parts melamine resin and weight portion are 0～10 part mixes with weight portion;
(2) add base metal salt again, stir 10～60 min, make base metal salt be dissolved in the melamine resin performed polymer fully, form the liquid of homogeneous;
(3) acid is added in the solution of step (2) gained and transfer to pH value 1～4, static 10 min ~ 24 h, after treating to solidify fully, the reduced vacuum drying obtains the melamino-formaldehyde xerogel that bulk contains base metal salt;
(4) the melamino-formaldehyde xerogel that the gained bulk is contained base metal salt heat treatment under 600～900 ℃ of conditions in inert atmosphere promptly obtains spherical nitrogen-doped carbon and carries the non noble metal oxygen reduction eelctro-catalyst.
7. a kind of spherical nitrogen-doped carbon according to claim 6 carries the preparation method of non noble metal oxygen reduction catalyst, it is characterized in that, described inert atmosphere is: Ar or He or N
2
8. a kind of spherical nitrogen-doped carbon according to claim 6 carries the preparation method of non noble metal oxygen reduction catalyst, it is characterized in that, the vacuum of described reduced vacuum drying is less than 0.09 MPa, and temperature is 20～50 ℃, and the time is 1～3 h.
9. a kind of spherical nitrogen-doped carbon according to claim 6 carries the preparation method of non noble metal oxygen reduction catalyst, it is characterized in that, described heat treatment time is 30～180 min.
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Application publication date: 20111123 |