CN105312087B - Nano-composite catalyst and preparation method and application - Google Patents

Nano-composite catalyst and preparation method and application Download PDF

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CN105312087B
CN105312087B CN201410366195.1A CN201410366195A CN105312087B CN 105312087 B CN105312087 B CN 105312087B CN 201410366195 A CN201410366195 A CN 201410366195A CN 105312087 B CN105312087 B CN 105312087B
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nano
alcohol
melamine
derivative
complex
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CN105312087A (en
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王远
刘岩
高昂
朱春梅
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Wuxi Shengxin Hydrogen Energy Technology Co ltd
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Peking University
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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

Abstract

The invention discloses a kind of nano-complex and preparation method thereof and the application as electrochemical catalyst.Nano-complex provided by the invention is substantially made up of melamine derivative, carbon material and transition metal or transition metal alloy nano-cluster, and carbon material includes at least one of conductive carbon black, activated carbon, carbon nanohorn, N doping carbon nanohorn, CNT, graphene, graphite and carbon fibre material；Metal nanometre cluster is selected from least one of Pt, Ru, Pd, Rh, Ir nano-cluster, the alloy nanocluster alloy nanocluster that two or more elements are formed in Pt, Ru, Pd, Rh, Ir, Au, Cu, Ni, the weight/mass percentage composition of transition metal or alloy nanocluster is 0.1 90%, and the size of transition metal or alloy nanocluster is 0.5 10 nanometers.As fuel-cell catalyst, the reactions such as nano-complex of the invention aoxidizes to hydrogen reduction and methanol have excellent electro catalytic activity.

Description

Nano-composite catalyst and preparation method and application
Technical field
The present invention relates to a kind of nano-composite catalyst and preparation method and application.
Background technology
Transition metal and its alloy nanocluster are a kind of nano materials with significant application value, a variety of available for developing Functional material and device (Y.Wang, Y.Wei, " Metal Nanoclusters " (Chapter) in H.S.Nalwa, Ed., Encyclopedia of Nanoscience and Nanotechnology,Vol.5,337-367,2004American Scientific Publishers), it is being catalyzed, energy conversion, environmental protection (vent gas treatment, purification of air etc.) etc. has And be widely applied very much prospect.Inventor once invented a kind of " non-protected type " noble metal and its alloy nanocluster and its Manufacture method, this kind of metal nanometre cluster is only by simple ion and organic solvent molecule used as stabilizers, and not only size is small, particle diameter distribution It is narrow, can in high volume synthesize, and by adding acidic aqueous solution, can easily by its from dispersion with the shape of precipitation Formula is separated and purified, and metal nanometre cluster precipitation can be scattered in again forms stable colloidal solution in many solvents (Y.Wang,J.Ren,K.Deng,L.Gui,Y.Tang,Chem.Mater.2000,12,1622；Chinese invention patent, ZL99100052.8), such metal nanometre cluster have been used for synthetic fuel cell catalyst electrode (Mao S., Mao G., Supported nanoparticle catalyst.USA Patent,US2003/0104936；Zhou W.,et al., App.Catal.B.2003,46,273)。
The noble-metal nanoclusters such as Pt, Ru play in fields such as chemical industry, petroleum refinement, petrochemistry, medicine, environmental protection and the energy Very important effect.It is expensive due to the scarcity of resources of the noble metals such as Pt, Ru, by by light transition metal and Pt, Ru etc. Noble-metal nanoclusters form binary or multicomponent alloy, can reduce the dosage of noble metal, while alloy has single metal institute not The specific function possessed.On the other hand, by metal and its alloy nanocluster and different carriers compound tense, carrier surface it is physico The interaction learned between property and metal/carrier can also play significant impact to catalytic performance.
The electrode catalyst used at present in Proton Exchange Membrane Fuel Cells (PEMFC) is mainly the catalysis of carbon loading platinum Agent (Pt/C).One of subject matter present in PEMFC practicalizations is the activation polarization problem of Pt/C catalyst, methanol The electrode reaction speed of the reaction such as oxidation and hydrogen reduction urgently further improves；There are some researches show pass through the method for alloying The some platinum base alloy catalyst (PtM/C) prepared have higher catalytic activity and anti-poisoning capability compared with Pt/C catalyst.
Metal and its alloy nanocluster are carried on carbon carrier, can generally use infusion process, reduction sedimentation, protection gold The methods of belonging to colloid absorption, Coordination Capture, deposition, embedding.Metal-carbon composite prepared by distinct methods has different micro- See structure, it is such as different form, different particle sizes and particle diameter distribution, these can be to the performance of metal-carbon composite Make a significant impact.There are some researches show the average grain diameter of Pt metal nanometre clusters is cloudy to PEMFC for the Pt/C catalyst of 3-5 nanometers Pole oxygen reduction reaction shows very high mass activity (K.Kinoshita, J.Electrochem.Soc.1990,137,845).It is existing There is technology to disclose the bimetallic catalysts such as a variety of carbon Supported Pt Nanoparticles-copper, wherein with 1：The carbon of 3 initial platinum/copper atom ratio carries The catalyst that platinum/copper bimetallic catalyst is prepared after electrochemical corrosion shows higher electro-catalysis to the reduction reaction of oxygen Activity.Strasser etc. is prepared for carbon using the method for dipping-high temperature reduction and carries Pt-Cu electrochemical catalysts, and they are by Pt/C Catalyst and Cu (NO3)2After water solution mixture freeze-drying, in high temperature (600,800,950 DEG C), 4%H2Reduced under atmosphere. When alloying temperature is low (600-800 DEG C), catalyst alloyization is incomplete, with the presence of simple substance Cu, can not be optimized Platinum/copper ratio.And when alloying temperature is high (such as 950 DEG C), metallic is assembled, and grows up, and has a strong impact on catalytic activity. This method be difficult to metal nanometre cluster composition and particle diameter it is simultaneously controllable, prepared catalytic performance still has much room for improvement (S.Koh and P.Strasser,J.Am.Chem.Soc.2007,129,12624)。
At present, one of subject matter present in carbon load alloy fuel cell catalyst is how to prepare alloy particle chi Very little small (being less than 5 nanometers), metal form controllable electrochemical catalyst.Tenor is very high (generally in fuel cell catalyst 10-50%), the solution of above mentioned problem is made there is very big challenge.
On the other hand, the interaction between carrier and metal has on catalyst catalytic performance and significantly affected, in fuel Usually using high-specific surface area carbon material with good conductivity in cell catalyst, to obtain larger metal ladings and metal point Divergence (E.Antolini, Applied Catalysis B:Environmental2009,88,1).But common conductive carbon Black, the materials such as CNT, graphite are dilute are not strong to the metal nanometre cluster adsorption capacity in colloidal solution, easily cause in metal-to-metal adhesive Noble-metal-supported efficiency is low during body is supported, and metal ladings are relatively low and easy the problems such as reuniting.
The content of the invention
It is an object of the invention to provide a kind of nano-complex catalyst and preparation method and application.
Nano-complex provided by the invention, including melamine derivative (MD), carbon material and nano-cluster；Wherein, structure Material into the nano-cluster is transition metal or transition metal alloy；
The quality of the nano-cluster accounts for the 0.1-90% of the nano-complex gross mass；
The mass ratio of the carbon material and melamine derivative is 1：1-100：1.
Above-mentioned nano-complex only can be also made up of said components.
The transition metal is selected from Pt, Ru, Pd, Rh and Ir at least one；Transition gold in the transition metal alloy Belong at least two in Pt, Ru, Pd, Au, Rh, Ir, Cu and Ni.
The particle diameter of the nano-cluster measured by electron microscope is 0.5 to 10 nanometer, concretely 0.5-2 nanometers； 0.5-5 nanometers, 0.5-10 nanometers, 1-5 nanometers；
The quality of the nano-cluster accounts for the 1-90% of the nano-complex gross mass, concretely 0.1%, 1%, 3%, 10%th, 16%, 19.2%, 20%, 27%, 27.8%, 28.9%, 30%, 40%, 41%, 50%, 59%, 60%, 80%, 85%th, 0.1-27%, 0.1-40%, 0.1-60%, 0.1-80% or 3-85%；
The mass ratio of the carbon material and melamine derivative is 5-30：1, concretely 1-30：1、1-50：1、3- 99：1；
The melamine derivative is selected from the derivative that melamine condensation polymer and melamine are formed with cyanuric acid At least one of.
In above-mentioned nano-complex, the melamine derivative (MD) include melamine condensation polymer and melamine with At least one of derivative that cyanuric acid is formed.
The N1s electron binding energies of the x-ray photoelectron spectroscopy (XPS) of the melamine condensation polymer are distributed mainly on 397 ~402eV scopes, in the XPS spectrum, N1s peaks include graphite N, skeleton N (- C=N-C) ,-NH2Include with the signal of amide groups Graphite N and amido (- NH2) N1s electron binding energies.
The melamine condensation polymer is prepared according to the method comprised the following steps：By melamine in fire-bar Polycondensation under part；In the heating condition, temperature is specially 573-973K.
The melamine condensation polymer is selected from least one of melem and melem condensation polymer；
The melamine includes melamine and the compound of cyanuric acid formation with the derivative that cyanuric acid is formed；
The production that the melamine is prepared with the derivative that cyanuric acid is formed including method in accordance with the following steps Thing：Melamine and cyanuric acid are mixed and heated with carbon material；The temperature of the heating is 278- 573K。
The melamine is answered with the derivative that cyanuric acid is formed including the hydrogen bond that melamine is formed with cyanuric acid Compound.
The melamine derivative absorption is chemically bound in carbon material surface and/or metal nanometre cluster surface.
The melamine derivative can adsorb or be chemically bound in carbon material surface formation melamine derivative and repair The carbon material (MDC) of decorations, the specific surface area of the carbon material (MDC) of the melamine derivative modification is 40-1300m2/ g, tool Body is 50-550m2/ g, 100-1300m2/ g, preferably nitrogen content 0.1-30wt%, 1-30wt%；
The carbon material of the melamine derivative modification includes the carbon material of melamine condensation polymer modification, and it is penetrated by X- The N1s electron binding energies that photoelectron spectra (XPS) measures are distributed mainly on 397~402eV scopes；
The carbon material of the melamine derivative modification also includes the compound that melamine is formed with cyanuric acid and repaiied The carbon material of decorations, its N1s electron binding energy measured by x-ray photoelectron spectroscopy (XPS) are distributed mainly on 397~403eV models Enclose.
The specific surface area of the carbon material is 40-2000m2/ g, concretely 60-1500m2/ g, 100-1500m2/g。
The carbon material is selected from conductive carbon black, activated carbon, N- doping carbon nanohorn, carbon nanohorn, CNT, graphite At least one of alkene, mesoporous carbon, graphite and carbon fibre material；
Nano-complex provided by the invention includes the compound with following feature：It is by x-ray photoelectron spectroscopy (XPS) the N1s electron binding energies measured are distributed mainly on 397~402eV scopes.
The method provided by the invention for preparing the nano-complex, namely method one, comprise the following steps：
1) solution of melamine is mixed with foregoing carbon material, is heat-treated after removing solvent, is cooled to room temperature, obtains To the carbon material MDC1 of melamine condensation polymer modification；
2) acid or soluble-salt of foregoing transition metal are dissolved in alcohol or alcohol-water mixture, it is 0.01- to obtain concentration 100g/L transistion metal compound solution, under agitation by above-mentioned solution and the alcohol of the hydroxide of alkali metal or alkaline-earth metal Solution or the aqueous solution or alcohol water mixed solution, the MDC1 of step 1) preparation is added, after blended, stirring or supersound process, Heated in reducing atmosphere or inert atmosphere in 313-600K, separate and collect the solid in system, obtain the nano-complex.
In the step 1) of the above method, the concentration of melamine solution is 1 × 10-3~102G/L, solvent are selected from water and energy Dissolve at least one of organic compound of melamine；Specifically it may be selected from the chemical combination such as water, alcohols, ketone, esters and ethers Thing or its mixture；
The mass ratio of the carbon material and melamine is 1：2~100：1, specially 1：2~40:1：1：1~9:1
The method for removing solvent is evaporation, centrifuges, filters or dry；
In the heat treatment step, atmosphere is inert atmosphere or oxygenous mixed gas；The temperature of heat treatment is 573- 973K；
In addition, after the step 1) is cooled to room temperature step, before step 2), products therefrom can also be washed Wash, cleaning solvent includes water or conventional organic solvent, including alcohol, nitrile, ketone equal solvent.
In the step 2), the alcohol is that C1-C8 monohydric alcohol, C1-C8 dihydric alcohol, C1-C8 dihydric alcohol spread out At least one of derivative of trihydroxylic alcohol of biology, C1-C8 trihydroxylic alcohol and C1-C8；
Wherein, the derivative of the dihydric alcohol of the C1-C8 is specially the unitary methoxy or ethoxy of C1-C8 dihydric alcohol Derivative；
The derivative of the trihydroxylic alcohol of the C1-C8 is specially that the unitary methoxy or ethoxy of C1-C8 trihydroxylic alcohol derives Thing；
In the alcohol-water mixture, the volumn concentration of water is 0-70%；Concretely 0-50%.
The reducing atmosphere is the atmosphere containing hydrogen.
In addition, in the step 2), in reducing atmosphere or inert atmosphere after 313-600K heating stepses, point Before the solid in collection system, for the ease of the separation of product, also acid solution can be added into gained mixture makes pH small In 7 and stirring the mixture for, stewing process.
Methods described also comprises the following steps：
The carbon material of the melamine derivative modification, and the step in this way are substituted with the nano-complex It is rapid 2) to be synthesized.
Present invention also offers a kind of method for preparing the nano-complex, namely method two, comprise the following steps：
The acid or soluble-salt of foregoing transition metal are dissolved in alcohol or alcohol-water mixture, it is 0.01- to obtain concentration 100g/L transistion metal compound solution, under agitation by it with alkali metal or the alcoholic solution of the hydroxide of alkaline-earth metal or The aqueous solution or alcohol solution mixing, according still further to proportioning by melamine condensation polymer and carbon materials described in gained liquid and this specification After material is mixed, stirred or is ultrasonically treated, heated in reducing atmosphere or inert atmosphere in 313-600K, separate and collect body Solid in system, obtain the nano-complex.
In the above method, the alcohol be C1-C8 monohydric alcohol, C1-C8 dihydric alcohol, C1-C8 dihydric alcohol derivative At least one of derivative of trihydroxylic alcohol of thing, C1-C8 trihydroxylic alcohol and C1-C8；
Wherein, the derivative of the dihydric alcohol of the C1-C8 is specially the unitary methoxy or ethoxy of C1-C8 dihydric alcohol Derivative；
The derivative of the trihydroxylic alcohol of the C1-C8 is specially that the unitary methoxy or ethoxy of C1-C8 trihydroxylic alcohol derives Thing；
In the alcohol-water mixture, the volumn concentration of water is 0-70%, concretely 0-50%.
The reducing atmosphere is the atmosphere containing hydrogen.
The mass ratio of the carbon material and melamine condensation polymer is 100：1-100；The quality of the carbon material and metal Than for 10：0.01-90.
The derivative that the melamine and cyanuric acid are formed is compound for melamine and hydrogen bond that cyanuric acid is formed Thing.
The N1s electron binding energies of the x-ray photoelectron spectroscopy of the nano-complex are distributed mainly on 397~403eV models Enclose.
In addition, separated and collected in reducing atmosphere or inert atmosphere after 300-600K heating stepses in system Before solid, for the ease of the separation of product, acid solution can be also added into gained mixture to be made pH be less than 7 and stirs mixture Mix, stewing process.
The melamine condensation polymer includes the product being prepared as follows：Melamine is set to contract in a heated condition It is poly-；In the heating condition, temperature 573-973K.
Present invention also offers a kind of method for preparing the nano-complex, namely method three, comprise the following steps：
1) a kind of in melamine and cyanuric acid is uniformly mixed with foregoing carbon material, then by melamine and trimerization Another kind in cyanic acid uniformly mixes with said mixture；Above-mentioned suspension is heat-treated, three are obtained after being cooled to room temperature The carbon material of poly cyanamid and cyanuric acid Derivatives Modified (MDC2)；
2) metallic colloid is prepared：By the soluble-salt of foregoing transition metal or the acid containing the transition metal be dissolved in alcohol or In alcohol-water mixture, the transistion metal compound solution that concentration is 0.01-100g/L is configured to, then adds alkali metal or alkaline earth The alcoholic solution or the aqueous solution or alcohol solution of the hydroxide of metal, gained mixed liquor is heated in 343-533K, obtained Cross metal nanometre cluster colloidal solution；
3) MDC2 obtained by step 1) is added into water-miscible organic solvent or its in the mixed solvent with water, ultrasound or It is dispersed with stirring obtained suspension；Transition metal nano-cluster colloidal solution obtained by step 2) and above-mentioned suspension are pressed into transition metal： MDC2 mass ratioes are 1：0.001-9 ratio mixing, stirring or supersound process, isolate precipitation and by it under 273-673K, Handled in inert atmosphere or reducing atmosphere or under reduced pressure, obtain the nano-complex.
In the step 1) of the above method, the method for the mixing includes will be a kind of molten in melamine and cyanuric acid Liquid uniformly mixes with the carbon material, removes the solvent in the mixture using the methods of volatilization, evaporation, filtering, by gained Mixture uniformly mixes with another solution in melamine and cyanuric acid, will using the methods of volatilization, evaporation, filtering Solvent in the mixture removes；The mixing or the temperature of removing solvent and heat treatment step are 273-573K；At the heat The atmosphere of reason process is inert atmosphere or oxygenous mixed gas；
The mass ratio of the melamine and cyanuric acid is 10：1 to 1：2；Melamine and the cyanuric acid solution Concentration be 0.1~102g/L；The solvent of the solution includes water and can dissolve the organic compound of melamine and cyanuric acid At least one of thing；The organic compound includes compound or its mixture such as alcohols, ketone, esters and ethers；In addition, Product can also be washed in the step, cleaning solvent includes water or conventional organic solvent, including alcohol, nitrile, ketone equal solvent；It is described The volumn concentration of mixed solvent reclaimed water is 0-90%；
In the step 2), the alcohol is that C1-C8 monohydric alcohol, C1-C8 dihydric alcohol, C1-C8 dihydric alcohol spread out At least one of derivative of trihydroxylic alcohol of biology, C1-C8 trihydroxylic alcohol and C1-C8；Wherein, the dihydric alcohol of the C1-C8 Derivative be specially C1-C8 dihydric alcohol unitary methoxy or ethoxy derivative；The derivative of the trihydroxylic alcohol of the C1-C8 Thing is specially the unitary methoxy or ethoxy derivative of C1-C8 trihydroxylic alcohol；
In the alcohol-water mixture, the volumn concentration of water is 0-70%, concretely 0-50%.
In the step 3), the precipitation of isolating includes being separated in a manner of filtering or centrifuge.
Methods described also comprises the following steps：
The carbon material of the melamine derivative modification, and the step in this way are substituted with the nano-complex It is rapid 3) to be synthesized.
In addition, in three kinds of preparation methods of the present invention, the melamine is substituted with nano-complex prepared by the present invention The carbon material of amine derivative modification, and the product synthesized by the step falls within protection scope of the present invention；This replacement shape Into synthetic method also fall within protection scope of the present invention.
The nano-complex of the present invention also includes receiving to the alloy nanocluster of cupric and/or nickel obtained by above-mentioned three kinds of methods Rice compound carries out prepared by chemical attack is to remove the light transition metal in part product.
The chemical attack includes using acid treatment, and the acid is at least one of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid.
The present invention also provides a kind of carbon material (i.e. MDC1 and MDC2) of melamine derivative modification and preparation method thereof.
In addition, as the fuel cell electrochemical catalyst of active ingredient and it is somebody's turn to do using above-mentioned nano-complex provided by the invention Application of the nano-complex in fuel cell electrochemical catalyst is prepared, falls within protection scope of the present invention.Wherein, it is described Fuel cell includes hydrogen reduction fuel cell or methanol oxidation fuel cells.
Melamine is a kind of heterocyclic compound with extensive use, and under heating state, melamine can occur one The polycondensation reaction of series, produce product (the L.Costa and such as close white amine, Miller amine, Miller amine condensation polymer and C3N4 G.Camino,J.Therm.Anal.,1988,34,423).Melamine acts on easily being formed with cyanuric acid is insoluble in answering for water Compound, there is abundant hydrogen bond network and nano aperture (Klaus Huthmacher, Dieter Most " in compound Cyanuric Acid and Cyanuric Chloride"Ullmann's Encyclopedia of Industrial Chemistry"2005,Wiley-VCH,Weinheim.ISBN10.1002/14356007.a08191).The present invention proposes to utilize Melamine derivative, i.e. compound of melamine condensation polymer, melamine and cyanuric acid etc. modify carbon material surface, borrow The interaction of aided metal nano-cluster and melamine derivative, the supported of metal nanometre cluster colloidal particle is set to be easy to carry out, Suppress nanoparticle aggregation to grow up, improve the catalytic performance of catalyst.Simultaneously it was found that in prepared compound, three Synergy between paracyanogen amine derivative and platinum group metal nano-cluster be present, this makes its intrinsic catalytic activity to oxygen reduction reaction Significantly improve.
It is small to prepare metal particle diameter, narrowly distributing, and alloy forms controllable high carrying capacity noble metal fuel cell catalyst to carrying The activity of high catalyst, increase chemical energy-electric energy conversion efficiency is significant, and is attempted to what is solved for a long time Problem.The cooperative effect of fuel-cell catalyst carrier and metallic is unclear to the affecting laws of catalytic performance, at this Before invention, no example shows the carbon material and metal nanometre cluster by melamine derivative or melamine derivative modification The compound of composition has excellent electrocatalytic oxidation reducing property or electro-catalysis methanol oxidation susceptibility.
The present invention is using developing carrier (melamine derivative modification carbon material) and the metal and alloy particle Interaction, effectively inhibits the agglomeration of metal or alloy particle in catalyst, can also under high metal carrying capacity Make the particle diameter of metal and alloy and form controllable, obtain that metal and alloy nano particle particle diameter in catalyst be small, narrowly distributing, gram Take in conventional high carrying capacity fuel battery metal and alloy catalyst that metal nanoparticle size is big, formed the difficulty of skewness Topic.
The research of the present inventor shows, develops in catalyst, electricity between metal and the melamine derivative be present Sub- transferance and/or synergic catalytic effect, by the interaction between such special carrier and metal and cooperative effect, institute Invention catalyst towards oxygen reduction or methanol oxidation etc. fuel cell reaction show excellent catalyst activity, this be can not from Simply deduce toward knowledge.
For example, the nano-complex catalyst (Pt-Cu/MDC1-1) of the alloy nanocluster containing Pt-Cu prepared by embodiment 1 Mass activity (the dynamics current value at 0.9V vs.RHE is as evaluation index, 720A/gPt) to oxygen reduction reaction is business With 4 times of Pt/C-JM catalyst (Pt content 9.4wt%)；Pt-Cu alloy nanocluster nano-complexes prepared by embodiment 3 (the dynamics current value at 0.95V vs.RHE is used as to be commented mass activity of the catalyst (Pt-Cu/MDC1-3) to oxygen reduction reaction Valency index, 374A/gPt) it is 8 times of commercial Pt/C-JM catalyst (46A/gPt, Pt content 52wt%), its mass activity is far excellent PtCu catalyst is carried in previously reported carbon；PtRu alloy nanocluster nano-complex catalysts PtRu/ prepared by embodiment 4 MDC1-4 to the catalytic activity (0.55V vs.RHE) of methanol oxidation is commercial PtRu/C-JM catalysis electrodes 2.6 times.It is real Apply mass activity (0.9V of the Pt metal nanometre clusters complex catalyst (Pt/MDC2-1) prepared by example 14 to oxygen reduction reaction Dynamics current value at vs.RHE is 364A/gPt) it is 2 times of commercial Pt/C-JM catalysis electrodes (167A/gPt), gained matter Amount activity carries the peak of Pt catalyst far above the carbon reported before.However, Pt/MDC2-1 electrochemical surface area but compares The commercial catalyst low 62%, it is seen that part Pt surfaces are covered by melamine derivative, and the special work that the two is formed Property center has excellent latent active (specific activity), so as to the vital catalyst of practical application Mass activity is greatly improved.
Brief description of the drawings
Fig. 1 is prepared by raw material melamine (a), the melamine condensation polymer MD1 (b) of the preparation of comparative example 1 and embodiment 1 The carbon material MDC1-1 (c) of melamine condensation polymer modification x-ray photoelectron spectroscopy (N1s).Graphite C 1s combination energy 284.5eV。
The powder X-ray that Fig. 2 (a) is Pt-Cu alloy nanocluster complex catalysts Pt-Cu/MDC1-1 prepared by embodiment 1 is penetrated Line diffraction spectra, Cu target K α；(b) x-ray photoelectron spectroscopy (N1s) for being Pt-Cu/MDC1-1, graphite C 1s combination energy 284.5eV。
Fig. 3 is Pt-Cu alloy nanocluster complex catalysts Pt-Cu/MDC1-1 prepared by embodiment 1 electromicroscopic photograph.
Fig. 4 is Pt-Cu alloy nanocluster complex catalyst Pt-Cu/MDC1-1 and commercially available Pt/C- prepared by embodiment 1 The catalytic activity of redox reactions on JM catalyst.
The Electronic Speculum that Fig. 5 is Pt-Cu alloy nanocluster complex catalysts Pt-Cu/MDC1-3 prepared by embodiment 3 is shone Piece.
Fig. 6 is Pt-Cu alloy nanocluster complex catalyst Pt-Cu/MDC1-3 and commercially available Pt/C- prepared by embodiment 3 The catalytic activity of redox reactions on JM catalyst.
Fig. 7 be the Derivatives Modified that melamine and cyanuric acid prepared by embodiment 14 is formed carbon material MDC2-1 and Pt/MDC2-1 N1s XPS spectrum, graphite C 1s is combined can 284.5eV.
Fig. 8 is the electromicroscopic photograph of Pt metal nanometre clusters complex catalyst (Pt/MDC2-1) prepared by embodiment 14.
Fig. 9 is that Pt metal nanometre clusters complex catalyst (Pt/MDC2-1) prepared by embodiment 14 is high in a nitrogen atmosphere Cyclic voltammetry curve in chloric acid aqueous solution (0.1M).
Figure 10 is the electromicroscopic photograph of Pt metal nanometre clusters complex catalyst (Pt/MDC2-2) prepared by embodiment 15.
The melamine and cyanuric acid that Figure 11 is raw material cyanuric acid CA (a), prepared by melamine (b), embodiment 15 The carbon material MDC2-2 (c) and Pt metal nanometre cluster complex catalyst Pt/MDC2-2 (d) of the Derivatives Modified of formation N1s XPS spectrum, graphite C 1s is combined can 284.5eV.
Figure 12 is melamine condensation polymer MD1 prepared by comparative example 1 infrared absorption spectroscopy.
Embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute It is conventional method unless otherwise instructed to state method.The raw material can obtain from open commercial sources unless otherwise instructed.
Embodiment 1, prepare the Pt-Cu alloy nanocluster complex catalysts Pt-Cu/MDC1-1 that tenor is 16wt% (method one)
0.1g melamines are dissolved in 100mL water, melamine solution is made.Conductive carbon black is (commercially availableXC-72R, 0.4g, specific surface area 254m2/ g) add in above-mentioned melamine solution, it is ultrasonically treated 20 minutes, in In 150 DEG C of oil baths heating boil off aqueous solvent, obtain melamine-carbon material (XC-72R) mixture.In air gas Under atmosphere, mixture is heated to 613K in Muffle furnace, room temperature is cooled to after being incubated 1h, obtain the modification of melamine condensation polymer Carbon material MDC1-1, elementary analysis show that nitrogen content is 4.4% in MDC1-1.BET specific surface area tests the ratio for showing MDC1-1 Surface area is 100m2/g。
Raw material melamine Melamine (a), melamine condensation polymer MD-1 prepared by comparative example 1 are compared in accompanying drawing 1 (b) the carbon material MDC1-1 (c) modified with melamine condensation polymer N1s XPS spectrums.In melamine XPS spectrum, N1s electronics knots Conjunction can be distributed mainly on 396.5-401eV scopes, be skeleton N (- C=N-C) and terminal amido (- NH2) nitrogen containing species signal； And MD-1 and MDC1-1 N1s electron binding energies are distributed mainly on 396-402eV scopes.Compared with MD-1, MDC1-1XPS spectrums exist There is an acromion at 399.8eV, it is combined can be compared with the combination high 0.6eV of energy of terminal amido in MD-1, with N1s combinations energy in amido link Unanimously, the intermediate product MD-1 terminal amido and the carboxyl hair on Vulcan XC-72R surfaces formed in MDC1-1 synthesis is shown Condensation reaction has been given birth to, has formed amido link.
31.1mg six is hydrated chloroplatinic acid and 26.5mg hydration copper acetate Cu (CH3COO)2·H2O is dissolved in 50ml ethylene glycol In, with NaOH ethylene glycol solution (0.25mol/L) by the pH value regulation of above-mentioned solution to 10, by gained mixed liquor under agitation It is added in the 80ml ethylene glycol for being dispersed with 86.5mg MDC1-1, continues stirring 5 minutes at room temperature, gained reactant is existed Under nitrogen atmosphere, room temperature is cooled to after 573K is heated to reflux 4 hours.Mixture is filtered, solid is washed with water and ethanol and sinks Starch.Gained solid sediment is dried in vacuo 4h under 343K, that is, Pt-Cu alloy nanocluster complex catalysts Pt- is made Cu/MDC1-1。
Accompanying drawing 2a is the X-ray diffraction spectrum of Pt-Cu/MDC1-1 catalyst, wherein 42.1 °, 48.5 °, 71.8 ° and 86.9 ° Signals assignment in catalyst face-centred cubic structure Pt/Cu alloy nano particles (Pt/Cu atomic ratios be 29:71) (111), (200), diffraction maximum corresponding to (220) and (311) crystal face.There is no simple substance Pt and Cu signal in spectrogram, show that alloying is complete.
Fig. 2 b are Pt-Cu/MDC1-1 catalyst n 1s XPS spectrums, and its N1s electron binding energy is distributed mainly on 397~402eV Scope.
Transmission electron microscope (TEM) photo of Pt-Cu/MDC1-1 catalyst is as shown in Figure 3.In Pt-Cu/MDC1-1 catalyst In, metal nanoparticle is well dispersed on carrier, and its average grain diameter is 3.8 nanometers, and particle diameter distribution is 1.5-8.5 nanometers. Inductively coupled plasma atomic emission (ICP-AES) test analysis shows that Pt and Cu total metal contents are 16wt%, and Pt contents are 9.1wt%.
The preparation of catalysis electrode：Prepared Pt-Cu/MDC1-1 catalyst fines 10mg are weighed, in 5mL absolute ethyl alcohols It is ultrasonically treated, 100 μ L is added into above-mentioned dispersionSolution, continue to be ultrasonically treated 20 minutes.Inhaled with liquid-transfering gun Take the suspension of 20 μ L catalyst to be added drop-wise to glassy carbon electrode surface, dry 0.5 hour in atmosphere at room temperature, then under 393K very Sky is dried 1 hour, that is, Pt-Cu/MDC1-1 catalysis electrodes are made.The electrode is placed in perchloric acid (0.1M), in 0.05-1.2V (vs RHE) potential section carries out cyclic voltammetry scan activation process.
Measured in the perchloric acid solution (0.1M) of oxygen saturation, the catalyst hydrogen reduction after above-mentioned activation process The more commercially available Pt/C-JM of mass activity of reaction (is purchased from Johnson Matthey companies, platinum content：9.4wt%) catalyst is in phase Mass activity with the conditions of is high 4 times (table one, Fig. 4).In table one, dynamics current value is according to Koutecky-Levich formula Calculate, 0.9V data are derived from polarization curves of oxygen reduction.
The catalytic activity contrast of table one, Pt-Cu/MDC1-1 and the reaction of commercially available Pt/C-JM catalyst towards oxygen reduction
Test condition：Temperature：303K, the perchloric acid solution (0.1M) of oxygen saturation, sweep speed：5mV/s.
Embodiment 2, prepare the Pt-Cu alloy nanocluster complex catalysts Pt-Cu/MDC1-2 that tenor is 41wt%
(method one)
The carbon material MDC1-1 of melamine condensation polymer modification is prepared by the methods described of embodiment 1.
By 1g six be hydrated chloroplatinic acid be dissolved in it is standby in 50mL ethylene glycol.In 313K under agitation, by the water of 7.6mL six Chloroplatinic acid (0.31mmol) ethylene glycol solution is closed to add dissolved with the ethylene glycol solution (227mL) of 150mg copper acetate monohydrates, NaOH ethylene glycol solution (0.25mol/L) adjusts the pH to 10 of above-mentioned solution, stirs 30 minutes.Above-mentioned mixed liquor is added dropwise to It is dispersed with MDC1-1 (350mg) 324mL ethylene glycol solutions, in a nitrogen atmosphere, is cooled down after 471K is heated to reflux 4 hours To room temperature, filtering, washing, it is dried in vacuo 5 hours in 343K.Above-mentioned solid product 350mg is taken, is scattered in 324mL ethylene glycol, Under agitation, the chloroplatinic acid ethylene glycol solution that 12.93mL is configured is added, prepares suspension A.242.1mg mono- is hydrated acetic acid Copper is dissolved in 365mL ethylene glycol solutions, prepares solution B, B is added into A, and NaOH ethylene glycol solution is added dropwise into gained mixture (0.25mol/L), pH to 9 is adjusted, in a nitrogen atmosphere, room temperature is cooled to after 471K is heated to reflux 4 hours.By mixture mistake Filter, solid product is washed with water and ethanol.Gained solid product is dried in vacuo 4 hours under 343K, that is, is made described and contains Pt- The complex catalyst Pt-Cu/MDC1-2 of Cu alloy nanoclusters.ICP-AES analysis shows, Pt/Cu is former in Pt-Cu/MDC1-2 Son is than being 31:69, Pt metal ladings are 24.1wt%, and average grain diameter is 3.1 nanometers.
Embodiment 3, prepare the Pt-Cu alloy nanocluster complex catalysts Pt-Cu/ that tenor is 27.8wt% MDC1-3
By Pt-Cu/MDC1-2 catalyst (50mg) ultrasonic disperse prepared by embodiment 2 in 1M nitric acid (20mL), After 298K is stirred 20 hours, centrifuge and precipitation is washed with water to remove the acid of residual, gained solid product is in 298K vacuum Dry 3 hours, Pt-Cu alloy nanocluster complex catalysts Pt-Cu/MDC1-3 is made.ICP-AES analysis shows, Pt-Cu/ Pt/Cu atomic ratios are 72 in MDC1-3:28, Pt metal ladings are 24.7wt%.
The TEM photos of PtCu/MDC1-3 catalyst are as shown in Figure 5.In Pt-Cu/MDC1-3, metal nanoparticle Average grain diameter is 2.1 nanometers, and particle diameter distribution is 1.5-3.5 nanometers.
The Pt-Cu/MDC1-3 catalyst prepared by characterizing method testing example 3 and commercially available Pt/ as described in embodiment 1 C-JM catalyst (platinum contents：52wt%) to the electro catalytic activity of oxygen reduction reaction, as a result as shown in Figure 6, Pt-Cu/MDC1- The mass activity (the dynamics current value at 0.95V vs.RHE) of 3 catalytic oxidation-reductions reaction is 374A/gPt, far above commercially available Pt/C-JM catalyst (46A/gPt).
Embodiment 4, to prepare tenor be 28.9wt%Pt-Cu alloy nanocluster complex catalysts Pt-Cu/MDC1-4 (method one)
By gained Pt-Cu/MDC1-2 catalyst (50mg) ultrasonic disperse of embodiment 2 0.75M nitric acid (18mL), 0.1M Sulfuric acid (1mL), 0.03M hydrochloric acid (1mL) mixed solution in, be warming up to 300K, stir 4 hours, after being cooled to room temperature, centrifugation point From and precipitation is washed with water to remove the acid of residual, gained solid product is dried in vacuo 10 hours in 333K, and Pt-Cu alloys are made Nano-cluster complex catalyst Pt-Cu/MDC1-4.ICP-AES analysis shows, Pt/Cu atomic ratios are 70 in Pt-Cu/MDC1-4: 30, Pt metal ladings are 25.4wt%.Tem analysis shows that the average grain diameter of metal nanoparticle is 2.1 in PtCu/MDC1-4 Nanometer, particle diameter distribution is 1.5-3.5 nanometers.
Embodiment 5, prepare the PtRu alloy nanocluster complex catalysts PtRu/MDC1-5 that bullion content is 30wt% (method one)
10mg melamines are dissolved in 80mL ethanol, melamine solution is made.The azepine that direct-current arc is synthesized Change nanometer angle-graphite complex carbon material (400mg, specific surface area 680m2/ g, by Chinese invention patent application (application number： 2012062500461210) prepared by methods described) add in above-mentioned melamine solution, be ultrasonically treated 20 minutes, in 353K plus Heat boils off solvent, obtains melamine-aza nanometer angle-graphite carbon mix.In nitrogen and the mixed atmosphere (nitrogen of oxygen Gas：Oxygen partial pressure ratio is 4：1) under, mixture is heated to 623K in tube furnace, insulation is cooled to room temperature after 1.5 hours, obtained To the carbon material (MDC1-5) of melamine condensation polymer modification, elementary analysis shows that nitrogen content is 1.8% in MDC1-5, and it compares table Area is 540m2/g。
1.036g six is hydrated chloroplatinic acid and 0.415g ruthenium trichlorides are dissolved in 50ml ethylene glycol, takes 50ml NaOH's Ethylene glycol solution (1.0mol/L) is added thereto with vigorous stirring, continues stirring 5 minutes at room temperature, by gained reactant Flowed back 3 hours obtained Pt-Ru alloy nanoclusters colloidal solution in 453K, be cooled to that room temperature is standby, wherein metal (Pt, Ru) is dense Spend for 5.92g/L.
MDC1-5 (35mg) is added in 150ml acetone solvents, 30 minutes (frequency 59kHz) is ultrasonically treated, by 4.05ml Pt metal-Ru colloidal solution be added drop-wise under fast stirring in above-mentioned suspension, by above-mentioned mixed liquor continue ultrasound 30 minutes Afterwards, continue stirring 36 hours, filtering, gained sediment is placed in vacuum drying chamber, dried under 300K.The black that will be obtained Powder is in tube furnace, under nitrogen atmosphere, is heated to 523K, is incubated 1 hour, be cooled to after room temperature be washed with deionized it is heavy Form sediment to without Cl-Ion detects, and is dried overnight being deposited in vacuum drying chamber in 313K, and it is 30wt%'s that bullion content, which is made, PtRu alloy nanocluster complex catalysts PtRu/MDC1-4.ICP-AES test analysis shows, Pt/Ru in PtRu/MDC1-5 Atomic ratio be 1:1.Tem analysis shows that the average grain diameter of PtRu nano-particles is 1.9 nanometers in PtRu/MDC1-5, particle diameter point Cloth is 0.5-5.5 nanometers.
Catalysis electrode is prepared by the methods described of embodiment 1, in 333K, the sulfuric acid solution of the methanol containing 1M of nitrogen saturation In (0.5M), the mass activity (0.55V vs.RHE, 335mA/mgPtRu) of PtRu/MDC1-5 catalysis methanol oxidation reactions is business With 2.6 times of PtRu/C-JM (PtRu content 30wt%) catalyst (128mA/mgPtRu), show PtRu/MDC1-5 catalyst There is very high catalytic activity to methanol oxidation.
Embodiment 6, to prepare tenor be 3wt%Ru metal nanometre cluster complex catalyst Ru/MDC1-6 (method one)
10mg melamines are dissolved in 100mL acetone solns, melamine solution is made.Conductive black is (commercially available Ketjen Black, 0.4g, specific surface area 950m2/ g) add in above-mentioned melamine solution, it is ultrasonically treated 20 minutes, in 60 DEG C heating boils off solvent, obtains melamine-Ketjen Black carbon materials) mixture.Under an argon atmosphere, mixture is existed 773K is heated in Muffle furnace, insulation is cooled to room temperature after 20 minutes, obtains the carbon material MDC1- of melamine condensation polymer modification 6, elementary analysis shows that nitrogen content is 0.5wt% in MDC1-6, and its specific surface area is 850m2/g。
1g hydrate ruthenium trichlorides are dissolved in 50ml ethylene glycol, take 50ml NaOH ethylene glycol solution (0.5mol/L) Add with vigorous stirring in the ethylene glycol solution of ruthenium trichloride, continue stirring 5 minutes at room temperature, by gained reactant in nitrogen Air-flow flows back 3 hours obtained ruthenium metal nanometre cluster colloidal solution under conditions of in 453K, and it is standby to be cooled to room temperature, wherein Metal Ru concentration is 3.86g/L.
MDC1-6 (90mg) is added in 150ml acetone, is ultrasonically treated 30 minutes, by 0.75ml metal Ru colloidal solution It is added drop-wise under fast stirring in above-mentioned suspension, after above-mentioned mixed liquor is continued into ultrasound 30 minutes, continues stirring 12 hours, mistake Filter, wash precipitation three times with acetone, gained solid sediment is heat-treated one hour in nitrogen atmosphere under 573K, is ground and is spent Ion water washing is to without Cl-Ion is detected, and is dried after precipitation is washed with a small amount of ethanol in vacuum drying chamber under 333K Overnight, the Ru metal nanometre cluster complex catalysts Ru/MDC1-6 that bullion content is 3wt% is made.Tem analysis shows, Ru/ The average grain diameter of Ru metal nanoparticles is 1.4 nanometers in MDC1-6, and particle diameter distribution is 1-3 nanometers.
Embodiment 7, prepare the Pt-Rh-Ir alloy nanocluster complex catalysts Pt-Rh- that bullion content is 3wt% Ir/MDC1-7) (method one)
Method in reference literature prepare carbon fiber (Eve S.Steigerwalt, et al., J.Phys.Chem.B, 2002,106,760–766)。
1g melamines are dissolved in 300mL ethanol waters (ethanol/water volume ratio=1：1) in, melamine is made Amine aqueous solution.Above-mentioned carbon fiber (2.5g) is added in melamine solution, is ultrasonically treated 1 hour, heats and steams in 160 DEG C of oil baths Solvent is removed, obtains melamine-carbon fiber mixture.573K is heated the mixture in air atmosphere, it is cold after being incubated 1 hour But to room temperature, the carbon material (MDC1-7) of melamine condensation polymer modification is obtained, elementary analysis shows that nitrogen content is in MDC1-7 15wt%.
0.5179g six is hydrated into chloroplatinic acid, 0.0658g rhodium trichloride hydrates and 0.0882g hydrated iridium trichlorides to be dissolved in The mixed solution of 50ml ethylene glycol and glycerine (ethylene glycol/glycerin volume ratio=5：1) in, under agitation by 50ml NaOH Ethylene glycol solution (0.16mol/L) be added thereto, continue at room temperature stirring 5 minutes, by gained reactant nitrogen protect Flowed back 3 hours in 473K under shield and " non-protected type " Pt-Rh-Ir alloy nanocluster colloids are made, it is standby to be cooled to room temperature, wherein gold The concentration for belonging to Pt-Rh-Ir is 2.69g/L.
Pt-Rh-Ir alloy nanocluster colloids obtained by 23ml are taken, 0.5mol/L sulfuric acid 95ml is added thereto, metal is received It is redispersed in re-forming Pt-Ru-Ir alloy nanocluster colloids in 25ml tetrahydrofurans after rice cluster precipitation and centrifugal separation, then will Gained Pt-Ru-Ir alloy nanoclusters colloid be added under fast stirring 20ml be dispersed with the above-mentioned MDC1-7 of 2g ethanol it is water-soluble (ethanol/water volume ratio=1 in liquid：1) stirring 10 hours, is continued, adding formic acid makes system pH be 3, precipitation is centrifuged, with water Washing, it is dried in vacuo 12 hours in 353K, that is, the Pt-Rh-Ir alloy nanocluster compounds that bullion content is 3wt% is made and urge Agent Pt-Rh-Ir/MDC1-7.Tem analysis shows, the average grain diameter of Pt-Rh-Ir alloy nanoclusters in Pt-Rh-Ir/MDC1-7 For 2 nanometers, particle diameter distribution is 1-4 nanometers, EDX analysis shows Pt-Rh-Ir alloy nano particles Pt：Rh：Ir atomic ratio is 4： 1：1.
Two or more in Pt, Rh, Ru, Ir etc. soluble-salt or acid are selected, using side similar to Example 7 Method, the alloy nanocluster complex catalyst containing these transition metal can be prepared.
Embodiment 8, the Pt-Cu-Pd alloy nanocluster complex catalysts Pt-Cu-Pd/ for preparing tenor 19.2wt% MDC1-8 (method one)
100mg melamines are dissolved in 80mL ethanol, melamine solution is made.Will be aza described in embodiment 3 Nanometer angle-graphite complex carbon material (50mg) is added in melamine solution, is ultrasonically treated 20 minutes, is boiled off in 353K heating molten Agent, obtain melamine-nanometer angle-graphite complex carbon material mixture.In a nitrogen atmosphere, 673K is heated the mixture to, Insulation is cooled to room temperature after 0.5 hour, obtains the carbon material MDC1-8 of melamine condensation polymer modification, and elementary analysis shows Nitrogen content is 18% in MDC1-8.
31mg six is hydrated chloroplatinic acid, 26.5mg hydration copper acetate Cu (CH3COO)2·H2O and 1mg palladiums are dissolved in In 50ml ethylene glycol, the pH value of above-mentioned solution is adjusted to 10 with NaOH ethylene glycol solution (0.25mol/L), gained is mixed Liquid is added in the 80ml ethylene glycol for being dispersed with 90mg MDC1-8 under agitation, continues stirring 5 minutes at room temperature, by gained Reactant in a nitrogen atmosphere, room temperature is cooled to after 573K is heated to reflux 4 hours.Mixture is filtered, washed with water and ethanol Wash solid sediment.Gained solid product is dried in vacuo 4h under 343K, that is, Pt-Cu-Pd alloy nanocluster compounds are made Catalyst Pt-Cu-Pd/MDC1-8.Tem analysis shows that the average grain diameter of alloy nano particle is in Pt-Cu-Pd/MDC1-8 4.0 nanometers, particle diameter distribution is 1-10 nanometers.ICP-AES analysis shows, Pt：Cu：Pd atomic ratio is 34:63:3.
Embodiment 9, prepare the Pt metal nanometre cluster complex catalysts Pt/MDC1-9 that tenor is 1wt%
60mg melamines are dissolved in 80mL water, melamine solution is made.Conductive carbon black is (commercially available XC-72R, 100mg, specific surface area 254m2/ g) add in above-mentioned melamine solution, it is ultrasonically treated 30 minutes, in 150 DEG C of oil In bath heating boil off aqueous solvent, obtain melamine-carbon material (XC-72R) mixture.In air atmosphere, will Mixture is heated to 623K, and insulation is cooled to room temperature after 40 minutes, obtains the carbon material MDC1-9 of melamine condensation polymer modification, Elementary analysis shows that nitrogen content is 11% in MDC1-9, and its specific surface area is 80m2/g。
0.1g six is hydrated into chloroplatinic acid to be dissolved in 50ml ethylene glycol, takes the aqueous solution (0.077mol/ of 50ml sodium hydroxides L), add under agitation in the ethylene glycol solution of chloroplatinic acid, continue stirring 25 minutes in room temperature, gained reactant is protected in nitrogen It is heated to reflux in 423K oil baths " non-protected type " platinum nano-cluster colloid being made in 4 hours under shield, it is standby to be cooled to room temperature, its The concentration of middle Pt metal is 0.375g/L.Tem analysis shows, the average grain diameter of Pt metal nanometre clusters in platinum nano-cluster colloid For 2.4 nanometers, particle diameter distribution is 1.5-4.5 nanometers.
Pt nano-cluster colloids obtained by 5.4ml are taken, 1mol/L formic acid 5ml are added thereto, by metal nanometre cluster pelleting centrifugation It is scattered in again in 5ml tetrahydrofurans after separation, gained metal nanometre cluster colloid is added drop-wise into 20ml under fast stirring disperses In the acetone for having MDC1-9 (0.2g), continue stirring 5 hours, precipitation is centrifuged, washed after 353K air dryings 12 Hour, that is, the Pt metal nanometre cluster complex catalysts Pt/MDC1-9 that platinum content is 1wt% is made.Tem analysis shows, Pt/ The average grain diameter of Pt nano-particles is 2.5 nanometers in MDC1-9, and particle diameter distribution is 1.5-5 nanometers.
Embodiment 10, prepare the Pt metal nanometre cluster complex catalysts Pt/MDC1-10 that tenor is 1wt%
5mg melamines are dissolved in 150mL water, melamine solution is made.By conductive carbon black (commercially available acetylene carbon black Denka black AB, 0.5g, specific surface area 60m2/ g) add in above-mentioned melamine solution, it is ultrasonically treated 20 minutes, in Heating boils off aqueous solvent in 150 DEG C of oil baths, obtains melamine-carbon material (Denka black AB) mixture.In air gas Under atmosphere, mixture is heated to 603K in Muffle furnace, insulation is cooled to room temperature after 1 hour, obtains melamine condensation polymer and repair The carbon material MDC1-10 of decorations, elementary analysis show that nitrogen content is 0.1% in MDC1-10, and its specific surface area is 50m2/g。
As described in Example 9, replace MDC1-9 to prepare the Pt metal nanometre clusters that platinum content is 1wt% with MDC1-10 to answer Mixture catalyst Pt/MDC1-10.Tem analysis shows that the average grain diameter of Pt nano-particles is 2.6 nanometers in Pt/MDC1-10, grain Footpath is distributed as 1.5-5.5 nanometers.
Embodiment 11, prepare the Pt metal nanometre clusters complex catalyst (Pt/MDC1-11) that Pt contents are 50wt%
(method two)
1g six is hydrated into chloroplatinic acid to be dissolved in 50ml ethylene glycol, takes 50ml NaOH ethylene glycol solution (0.5mol/L) Add under agitation in the ethylene glycol solution of chloroplatinic acid, continue stirring 5 minutes at room temperature, gained reactant is circulated in nitrogen Under conditions of crossing, flowed back 3 hours in 453K and " non-protected type " platinum nano-cluster colloidal solution is made, it is standby to be cooled to room temperature, Wherein the concentration of Pt metal is 3.7g/L.
1g melamines are heated to 623K in a nitrogen atmosphere in Muffle furnace, insulation is cooled to room temperature after 40 minutes and obtained To melamine condensation polymer MD-2.Under agitation, MD-2 (10mg) is added to 80ml ethylene glycol solution, NaOH is added dropwise thereto Ethylene glycol solution (0.25mol/L), regulation pH value of solution is heated to 443K to 10, and insulation is cooled to room temperature after 30 minutes, stirred Mix lower by conductive black (commercially available Black pearls2000,40mg, specific surface area 1500m2/ g) add in above-mentioned mixed liquor, surpass Sonication 20 minutes.13.5ml Pt metal colloidal solution is added drop-wise in above-mentioned suspension under fast stirring, to above-mentioned mixed Close liquid be ultrasonically treated within 20 minutes, stir 36 hours, filtering, be washed with deionized and be precipitated to no Cl-Ion is detected, will Gained solid sediment is dried in vacuo 5 hours under 353K, that is, Pt metal nanometre cluster complex catalysts Pt/MDC1-11 is made. ICP-AES test analysis shows that Pt contents are 50wt% in Pt/MDC1-11 catalyst.Tem analysis shows, in Pt/MDC1-10 The average grain diameter of Pt metal nanoparticles is 2.4 nanometers.Elementary analysis shows that nitrogen content is 5.5wt% in Pt/MDC1-11.
Embodiment 12, prepare the Pt metal nanometre clusters complex catalyst (Pt/MDC1-12) that Pt contents are 59wt%
(method two)
" non-protected type " Pt nano-clusters colloidal solution and melamine condensation polymer MD-2 are prepared as described in Example 11.
Under agitation, MD-2 (20mg) is added to 120ml ethylene glycol solution, with NaOH ethylene glycol solution (0.25mol/L) adjusts the pH value of above-mentioned mixed solution to 10, is heated to 443K, insulation is cooled to room temperature after 30 minutes. By conductive black (commercially available Black pearls2000,20mg, specific surface area 1500m under stirring2/ g) add in above-mentioned mixed liquor, It is ultrasonically treated 1 hour.16.2ml Pt metal colloidal solution is added drop-wise in above-mentioned suspension under fast stirring, to above-mentioned mixed Close liquid be ultrasonically treated within 30 minutes, stir 48 hours, add 10ml formic acid solutions (1mol/L), continue to be stirred vigorously 24 small When, filtering, it is washed with deionized and is precipitated to no Cl-Ion is detected, and gained solid sediment is dried in vacuo into 1 under 353K Hour, that is, Pt metal nanometre cluster complex catalysts Pt/MDC1-12 is made.ICP-AES test analysis shows, Pt/MDC1-12 Middle Pt contents are 59wt%.Tem analysis shows that the average grain diameter of Pt metal nanoparticles in Pt/MDC1-12 is 2.5 nanometers, grain Footpath is distributed as 1-6.5 nanometers.Elementary analysis shows that nitrogen content is 12wt% in Pt/MDC1-12.
Embodiment 13, to prepare tenor be 20wt%Pt-Ni alloy nanocluster complex catalysts (Pt-Ni/MDC1- 13) (method two)
0.1g melamines are heated to 733K in air atmosphere in Muffle furnace, insulation is cooled to room temperature after 1 hour Obtain melamine condensation product MD-4.
65.6mg six is hydrated chloroplatinic acid and 1mg Ni (CH3COO)2·4H2O is dissolved in 60ml ethylene glycol, with NaOH's Ethylene glycol solution (0.25mol/L) adjusts the pH value of above-mentioned mixed solution to 10, mixed liquor is added under agitation containing In the ethylene glycol (80ml) of CNT (50mg), graphene (50mg) and MD-4 (24mg), said mixture is placed in microwave In synthesizer water heating kettle, in a nitrogen atmosphere, 333K is warming up to, is incubated 10 minutes, gas in reaction gas is changed into containing 1% hydrogen The nitrogen of gas, then temperature is risen into 523K, it is cooled to room temperature after 523K reacts 3 minutes.Mixture is filtered, with water and ethanol Wash solid sediment.Gained solid sediment is dried in vacuo 5 hours under 323K, that is, tenor is made and is closed for Pt-Ni Gold nanoclusters complex catalyst Pt-Ni/MDC1-14.Tem analysis shows, Pt-Ni metallic nanoparticles in Pt-Ni/MDC1-14 The average grain diameter of son is 2 nanometers, and particle diameter distribution is 1-5 nanometers.EDX test analysis shows that Pt/Ni is former in Pt-Ni/MDC1-14 Son is than being 9:1, elementary analysis shows that nitrogen content is 8wt% in Pt-Ni/MDC1-14.
Embodiment 14, the Pt metal nanometre clusters complex catalyst (Pt/MDC2-1) for preparing tenor 10wt%
(method three)
" non-protected type " Pt nano-cluster colloidal solution is prepared as described in Example 11.
Melamine (12.5mg) and cyanuric acid (12.5mg) are dissolved separately in 80mL water.By conductive carbon black (business PurchaseXC-72R, 100mg, specific surface area 254m2/ g) add in above-mentioned melamine solution, it is ultrasonically treated 30 minutes, In 423K oil baths heating boil off aqueous solvent, obtain melamine-carbon material (XC-72R) mixture.Gained is consolidated Body mixture is added in cyanuric acid solution, is ultrasonically treated 1 hour, and solvent is boiled off in 423K heating.Solid product is added In 500mL deionized waters, ultrasonic 20min, it is heated to 323K and keeps the temperature to stir 1 hour, washing removes excessive trimerization Cyanic acid or melamine.After the completion of washing, filter and dry filter cake 8 hours under 323K, vacuum condition, obtain melamine The carbon material MDC2-1 of the Derivatives Modified formed with cyanuric acid.Elementary analysis shows that nitrogen content is 10wt% in MDC2-1, Its specific surface area is 110m2/g。
MDC2-1 (90mg) is added into the 200ml aqueous solution, is ultrasonically treated 10 minutes.By 2.7ml Pt metal colloidal solution It is added drop-wise in above-mentioned suspension, stirs 12 hours under fast stirring, filtering, is washed with deionized and is precipitated to no Cl-Ion It is detected.Gained solid product is dried in vacuo 1 hour in 323K, and Pt metal nanometre cluster complex catalysts Pt/MDC2-1 is made.
Accompanying drawing 7 is MDC2-1 and Pt/MDC2-1 N1s XPS spectrum.MDC2-1 N1s electron binding energies are distributed mainly on 397-403eV scopes.Pt/MDC2-1 N1s electron binding energies are distributed mainly on 396-402eV scopes.
ICP-AES test analysis shows that Pt contents are 10wt% in Pt/MDC2-1.Tem analysis shows, in Pt/MDC2-1 The average grain diameter of Pt metal nanoparticles is 2.0 nanometers, and particle diameter distribution is 0.5-4.5 nanometers (Fig. 8).
Catalysis electrode is prepared by method described in embodiment 1, in perchloric acid (0.1M) aqueous solution of 303K nitrogen saturations Test the cyclic voltammogram (Fig. 9) of Pt/MDC2-1 and the Pt/C catalyst prepared by comparative example 2.Occur to owe on Pt surfaces by hydrogen The electricity of potential deposition suction/desorption calculates the electrochemical surface area (ECSA) of Pt in catalyst.Pt/MDC2-1 and Pt/C catalysis The ECSA of agent is respectively 24 and 75m2/gPt.Pt contents are 10wt% in two kinds of catalyst, and Pt nano-particles sizes differ Less, and Pt/MDC2-1 ECSA is only the 32% of Pt/C catalyst, is illustrated in Pt/MDC2-1 building-up processes, part Pt receives Rice corpuscles surface is covered by the derivative that melamine and cyanuric acid are formed so that Pt/MDC2-1 ECSA is greatly decreased.
What the Pt/MDC2-1 catalyst towards oxygen reduction as described in embodiment 1 prepared by method testing example 14 reacted Electro catalytic activity, Pt/MDC2-1 are to the mass activity (the dynamics current value at 0.9V vs.RHE) of oxygen reduction reaction 364A/gPt, it is commercial Pt/C-JM catalyst (167A/gPt, Pt content 9.4wt%, ECSA 87m2/ gPt) 2 times, be institute Prepare 1.7 times of Pt/C catalyst (214A/gPt).Although Pt/MDC2-1 ECSA is only Pt/C-JM and Pt/C 30% left side The right side, but Pt/MDC2-1 is far above Pt/C-JM and Pt/C catalyst to the mass activity of oxygen reduction reaction, shows in Pt/MDC2-1 In catalyst, synergic catalytic effect between Pt nano-particles and the melamine derivative be present, form high catalytic activity body System.
Embodiment 15, prepare Pt metal nanometre clusters complex catalyst (the Pt/MDC2-2) (side that tenor is 30wt% Method three)
" non-protected type " Pt nano-cluster colloidal solution is prepared as described in Example 11.
Melamine (55mg) and cyanuric acid (55mg) are dissolved separately in (body of water in 100mL alcohol water mixed solutions 50%) product percentage composition is.By commercially available conductive carbon black (Black Pearl2000,400mg, specific surface area 1500m2/ g) plus Enter in melamine solution, be ultrasonically treated 20 minutes, boil off solvent in 403K heating, gained solid is added into cyanuric acid solution In, it is ultrasonically treated 1 hour, boils off solvent in 403K heating, gained solid is washed with water, and dried 12 hours under 353K, obtain The carbon material MDC2-2 of the Derivatives Modified formed to melamine and cyanuric acid.Elementary analysis shows nitrogen content in MDC2-2 For 11wt%.
MDC2-2 (70mg) is added in 150ml water, is ultrasonically treated 10 minutes.8.1ml Pt metal colloidal solution is existed It is added drop-wise in above-mentioned suspension, stirs 36 hours under quick stirring, filters, is washed with deionized and is precipitated to no Cl-Ion quilt Detection.Gained solid product is dried in vacuo 5 hours in 313K, and Pt metal nanometre cluster complex catalysts Pt/MDC2-2 is made. ICP-AES test analysis shows that Pt contents are 30wt% in Pt/MDC2-2.The tem analysis of accompanying drawing 10 shows, in Pt/MDC2-2 The average grain diameter of Pt metal nanoparticles is 1.7 nanometers, and particle diameter distribution is 0.5-6 nanometers.
MDC2-2 and Pt/ prepared by raw material cyanuric acid CA (a), melamine (b), embodiment 14 are compared in accompanying drawing 11 MDC2-2 (c) N1s XPS spectrum.The N1s electron binding energies of cyanuric acid are distributed mainly on 399-403eV scopes, and melamine The N1s electron binding energies of amine are distributed mainly on 397-401eV scopes, and the electron binding energy at summit is respectively 400.8 Hes 398.7eV.Different from above-mentioned two situations, the carbon material MDC2-2's for the Derivatives Modified that cyanuric acid and melamine are formed N1s electron binding energies are distributed mainly on 396-403eV scopes, and the electron binding energy at its summit is 399.6eV.Pt/MDC2-2 N1s electron binding energies be distributed mainly on 397-402eV scopes.Compared with MDC2-2, the electricity at Pt/MDC2-2 N1s summits Son combines energy (399.0eV) and moves 0.6eV to low electron binding energy.
Pt/MDC2-2 catalyst towards oxygen reduction as described in embodiment 1 prepared by characterizing method testing example 14 is anti- The electro catalytic activity answered, Pt/MDC2-2 are to the mass activity (the dynamics current value at 0.9V vs.RHE) of oxygen reduction reaction 320A/gPt, it is 1.9 times of commercial Pt/C-JM catalysis electrodes (167A/gPt).
Embodiment 16, prepare Pt metal nanometre clusters complex catalyst (Pt/MDC2-3) (method that Pt contents are 90wt% Three)
Melamine (60mg) and cyanuric acid (60mg) are dissolved separately in 100mL acetonitrile solutions.By commercially available conduction Carbon black (Black pearls2000,400mg) is added in cyanuric acid solution, is ultrasonically treated 20 minutes, is depressurized and is steamed under 333K Go out solvent, gained solid added in melamine solution, be ultrasonically treated 1 hour, volatilization is heated under 373K, remove solvent, Solid product is added in 500mL deionized waters, ultrasonic 30min, be heated to 333K and keep the temperature to stir 1 hour, washing, Filter and dry filter cake 12 hours under 333K, obtain the carbon material for the Derivatives Modified that melamine is formed with cyanuric acid MDC2-3.Elementary analysis shows that nitrogen content is 11.5wt% in MDC2-3.
" non-protected type " Pt nano-cluster colloidal solution is prepared as described in Example 11.
MDC2-3 (10mg) is added into the 200ml aqueous solution, is ultrasonically treated 10 minutes.By 24.3ml Pt metal colloidal solution It is added drop-wise in above-mentioned suspension, stirs 48 hours under fast stirring, pH to 3 is adjusted with aqueous formic acid, stirred 5 hours, mistake Filter, be washed with deionized and be precipitated to no Cl-Ion is detected.Gained solid product is dried in vacuo 8 hours in 343K, and Pt is made Metal nanometre cluster complex catalyst Pt/MDC2-3.ICP-AES test analysis shows that Pt contents are in Pt/MDC2-3 90wt%.Tem analysis shows that the average grain diameter of Pt metal nanoparticles is 3.6 nanometers in Pt/MDC2-3.
Comparative example 1,0.1g melamines are heated to 613K in air atmosphere in Muffle furnace, it is cold after being incubated 1 hour But melamine condensation polymer (MD-1) is made to room temperature.Elementary analysis (C32.96；N63.87, H2.75), infrared spectrum (figure 12) analysis shows, MD-1 are melem.MD-1 x-ray photoelectron spectroscopy (N1s) is shown in accompanying drawing 1.
Comparative example 2, the Pt metal nanometre clusters complex catalyst (Pt/C) for preparing tenor 10wt%
" non-protected type " Pt nano-cluster colloidal solution is prepared as described in Example 11.
Supporting Pt nano-cluster as described in Example 14, MDC2-1 is changed into commercially availableXC-72R, other steps It is identical, prepare Pt metal nanometre clusters complex catalyst (Pt/C).ICP-AES test analysis shows, Pt contents in Pt/C For 10wt%.Tem analysis shows that the average grain diameter of Pt metal nanoparticles is 2 nanometers in Pt/C, particle diameter distribution 0.5-4.5 Nanometer.
The cyclic voltammogram for the Pt/C catalyst tested in perchloric acid (0.1M) aqueous solution of 303K nitrogen saturations is shown in Accompanying drawing 9.
The electro catalytic activity reacted by the test Pt/C catalyst towards oxygen reduction of characterizing method described in embodiment 1, Pt/C pairs The mass activity (the dynamics current value at 0.9V vs.RHE) of oxygen reduction reaction is 214A/gPt.

Claims (42)

1. a kind of nano-complex, including melamine derivative, carbon material and nano-cluster；Wherein, the nano-cluster is formed Material is transition metal or transition metal alloy；
The quality of the nano-cluster accounts for the 0.1-90% of the nano-complex gross mass；
The mass ratio of the carbon material and melamine derivative is 1：1-100：1.
2. nano-complex according to claim 1, it is characterised in that：The nano-complex is spread out by the melamine Biology, carbon material and nano-cluster composition；
The transition metal is selected from Pt, Ru, Pd, Rh and Ir at least one；Transition metal choosing in the transition metal alloy From at least two in Pt, Ru, Pd, Au, Rh, Ir, Cu and Ni；
The particle diameter of the nano-cluster measured by electron microscope is 0.5 to 10 nanometer；
The quality of the nano-cluster accounts for the 1-60% of the nano-complex gross mass；
The mass ratio of the carbon material and melamine derivative is 5-30：1；
In the derivative that the melamine derivative is formed selected from melamine condensation polymer and melamine with cyanuric acid It is at least one.
3. nano-complex according to claim 2, it is characterised in that：The melamine derivative absorption or chemical bond Together in the surface of carbon material surface and/or the nano-cluster.
4. nano-complex according to claim 2, it is characterised in that：The melamine derivative absorption or chemical bond Together in carbon material surface, the carbon material that melamine derivative is modified is formed；The carbon material of the melamine derivative modification Specific surface area be 40-1300m2/g；Nitrogen content is 0.1-30wt%.
5. nano-complex according to claim 4, it is characterised in that：The nitrogen content is 1-30wt%.
6. nano-complex according to claim 2, it is characterised in that：The specific surface area of the carbon material is 40- 2000m2/g。
7. nano-complex according to claim 6, it is characterised in that：The specific surface area of the carbon material is 60- 1500m2/g。
8. nano-complex according to claim 2, it is characterised in that：The carbon material be selected from conductive carbon black, activated carbon, At least one of carbon nanohorn, CNT, graphene, mesoporous carbon, graphite and carbon fibre material.
9. nano-complex according to claim 8, it is characterised in that：The carbon nanohorn is that N- adulterates carbon nanohorn.
10. nano-complex according to claim 2, it is characterised in that：As described in measuring x-ray photoelectron spectroscopy The N1s electron binding energies of nano-complex are distributed mainly on 397~402eV scopes.
11. nano-complex according to claim 2, it is characterised in that：The melamine derivative is melamine Condensation polymer；
The N1s electron binding energies of the x-ray photoelectron spectroscopy of the melamine condensation polymer are distributed mainly on 397~402eV models Enclose.
12. nano-complex according to claim 11, it is characterised in that：In the x-ray photoelectron spectroscopy, N1s peaks Including graphite N ,-C=N-C ,-NH2With the signal of amide groups.
13. nano-complex according to claim 11, it is characterised in that：The melamine condensation polymer be according to including The method of following steps is prepared：By melamine polycondensation in a heated condition；
In the heating condition, temperature 573-973K.
14. nano-complex according to claim 11, it is characterised in that：The melamine condensation polymer be melem and At least one of melem condensation polymer.
15. nano-complex according to claim 2, it is characterised in that：The nano-complex is according to including as follows The method of step is prepared：
1) solution of melamine is mixed with any carbon materials of at least one claim 3-6, carried out after removing solvent Heat treatment, is cooled to room temperature, obtains the carbon material MDC1 of melamine condensation polymer modification；
2) acid or soluble-salt of any transition metal of at least one claim 1-4 are dissolved in alcohol or alcohol-water mixture In, the transistion metal compound solution that concentration is 0.01-100g/L is obtained, under agitation by above-mentioned solution and alkali metal or alkaline earth Alcoholic solution or the aqueous solution or the alcohol solution mixing of the hydroxide of metal, add step 1) gained melamine condensation polymer and repair The carbon material MDC1 of decorations, after blended, stirring or supersound process, adds in reducing atmosphere or inert atmosphere in 313-600K Heat, the solid in system is separated and collected, obtain the nano-complex.
16. nano-complex according to claim 15, it is characterised in that：In the step 1), the solution of melamine Concentration be 1 × 10-3~102G/L, solvent are selected from water and can dissolve at least one of organic compound of melamine；
The mass ratio of the carbon material and melamine is 1：2~100：1；
The method for removing solvent is evaporation, filtering or dry；
In the heat treatment step, atmosphere is inert atmosphere or oxygenous mixed-gas atmosphere；The temperature of heat treatment is 573- 973K；
In the step 2), the alcohol be C1-C8 monohydric alcohol, C1-C8 dihydric alcohol, C1-C8 dihydric alcohol derivative, At least one of C1-C8 trihydroxylic alcohol and the C1-C8 derivative of trihydroxylic alcohol；
The derivative of the dihydric alcohol of the C1-C8 is the unitary methoxy or ethoxy derivative of C1-C8 dihydric alcohol；
The derivative of the trihydroxylic alcohol of the C1-C8 is the unitary methoxy or ethoxy derivative of C1-C8 trihydroxylic alcohol；
In the alcohol-water mixture, the volumn concentration of water is 0-70%；
The reducing atmosphere is the atmosphere containing hydrogen.
17. nano-complex according to claim 16, it is characterised in that：In the alcohol-water mixture, the volume hundred of water Point content is 0-50%.
18. nano-complex according to claim 2, it is characterised in that：The nano-complex is according to including as follows The method of step is prepared：
The acid or soluble-salt of any transition metal of at least one claim 1-4 are dissolved in alcohol or alcohol-water mixture In, the transistion metal compound solution that concentration is 0.01-100g/L is obtained, under agitation by it with alkali metal or alkaline-earth metal Alcoholic solution or the aqueous solution or the alcohol solution mixing of hydroxide, according still further to proportioning by gained liquid and at least one claim After any melamine condensation polymers of 1-13 and carbon material are mixed, stirred or be ultrasonically treated, in reducing atmosphere or lazy Property atmosphere in 313-600K heat, separate and collect the solid in system, obtain the nano-complex.
19. nano-complex according to claim 18, it is characterised in that：The alcohol is C1-C8 monohydric alcohol, C1- C8 dihydric alcohol, the derivative of C1-C8 dihydric alcohol, C1-C8 trihydroxylic alcohol and C1-C8 trihydroxylic alcohol derivative at least It is a kind of；
The derivative of the dihydric alcohol of the C1-C8 is the unitary methoxy or ethoxy derivative of C1-C8 dihydric alcohol；
The derivative of the trihydroxylic alcohol of the C1-C8 is the unitary methoxy or ethoxy derivative of C1-C8 trihydroxylic alcohol；
In the alcohol-water mixture, the volumn concentration of water is 0-70%；
The reducing atmosphere is the atmosphere containing hydrogen；
The mass ratio of the carbon material and melamine condensation polymer is 100：1-100；The mass ratio of the carbon material and metal is 10：0.01-90.
20. nano-complex according to claim 19, it is characterised in that：In the alcohol-water mixture, the volume hundred of water Point content is 0-50%.
21. nano-complex according to claim 2, it is characterised in that：The melamine is formed with cyanuric acid Derivative is the bond complexes that melamine is formed with cyanuric acid.
22. nano-complex according to claim 21, it is characterised in that：The X-ray photoelectron of the nano-complex The N1s electron binding energies of power spectrum are distributed mainly on 397~403eV scopes.
23. nano-complex according to claim 21, it is characterised in that：The nano-complex is according to including as follows The method of step is prepared：
1) a kind of and any carbon materials of at least one claim 3-9 in melamine and cyanuric acid are uniformly mixed Close, then the another kind in melamine and cyanuric acid is uniformly mixed with said mixture；The product that above-mentioned mixing is obtained It is heat-treated, the carbon material MDC2 of melamine and cyanuric acid Derivatives Modified is obtained after being cooled to room temperature；
2) metallic colloid is prepared：By the soluble-salt of any transition metal of at least one claim 1-4 or containing the mistake The acid for crossing metal is dissolved in alcohol or alcohol-water mixture, is configured to the transistion metal compound solution that concentration is 0.01-100g/L, Then the alcoholic solution or the aqueous solution or alcohol solution of the hydroxide of alkali metal or alkaline-earth metal are added, gained mixed liquor is existed 343-533K is heated, and obtains the transition metal nano-cluster or alloy nanocluster colloidal solution；
3) MDC2 obtained by step 1) is scattered in water-miscible organic solvent or its in the mixed solvent with water, be made suspended Liquid；Transition metal nano-cluster colloidal solution obtained by step 2) and above-mentioned suspension are pressed into transition metal：MDC2 mass ratioes are 1： 0.001-9 ratio mixing, stirring or supersound process, isolate precipitation and by it under 273-673K, in inert atmosphere or also Heated in Primordial Qi atmosphere or under reduced pressure, obtain the nano-complex.
24. nano-complex according to claim 23, it is characterised in that：In the step 1), the method for the mixing For a kind of solution in melamine and cyanuric acid is uniformly mixed with the carbon material, using volatilization, evaporation, filtering side Method removes the solvent in the mixture, and gained mixture and another solution in melamine and cyanuric acid is uniform Mixing, using volatilization, evaporation or filter the solvent removing in gained mixture；The mixing, remove solvent or heat treatment step Rapid temperature is 273-573K；The atmosphere of the heat treatment process is inert atmosphere or oxygenous mixed gas；
The mass ratio of the melamine and cyanuric acid is 10：1 to 1：2；Melamine and the cyanuric acid solution it is dense Spend for 0.1~102g/L；The solvent of the solution is included in water and the organic compound that can dissolve melamine and cyanuric acid At least one；The organic compound includes alcohols, ketone, esters and ether compound or its mixture；
In the step 2), the alcohol be C1-C8 monohydric alcohol, C1-C8 dihydric alcohol, C1-C8 dihydric alcohol derivative, At least one of C1-C8 trihydroxylic alcohol and the C1-C8 derivative of trihydroxylic alcohol；Wherein, the derivative of the dihydric alcohol of the C1-C8 Thing is the unitary methoxy or ethoxy derivative of C1-C8 dihydric alcohol；The derivative of the trihydroxylic alcohol of the C1-C8 is C1-C8 Trihydroxylic alcohol unitary methoxy or ethoxy derivative；
In the alcohol-water mixture, the volumn concentration of water is 0-50%；
The precipitation of isolating includes being separated in a manner of filtering or centrifuge.
25. the nano-complex according to claim 15 or 23, it is characterised in that：Methods described also comprises the following steps：
The carbon material of the melamine derivative modification is substituted with nano-complex described in claim 2, and presses claim 14 steps 2) or claim 22 are stated step 3) and synthesized.
26. according to the nano-complex described in claim 15,18 or 23, it is characterised in that：Methods described also includes as follows Step：
The nano-complex of the cupric of the gained of claim 15,18 or 23 and/or the alloy nanocluster of nickel is subjected to chemical attack To remove the light transition metal in part.
27. nano-complex according to claim 26, it is characterised in that：The method of the chemical attack is with acid Reason, the acid include at least one of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid.
28. the nano-complex described in claim 3,15,18 or 23, it is characterised in that：The melamine derivative modification The specific surface area of carbon material be 40-1300m2/g。
29. nano-complex according to claim 28, it is characterised in that：The carbon materials of the melamine derivative modification The specific surface area of material is 50-1200m2/g。
30. nano-complex according to claim 28, it is characterised in that：The carbon materials of the melamine derivative modification The N1s peaks of the x-ray photoelectron spectroscopy of material cover 396~403.5eV scopes.
31. a kind of method for preparing nano-complex described in claim 2, comprises the following steps：
1) solution of melamine is mixed with any carbon materials of at least one claim 3-9, carried out after removing solvent Heat treatment, is cooled to room temperature, obtains the carbon material MDC1 of melamine condensation polymer modification；
2) acid or soluble-salt of any transition metal of at least one claim 1-4 are dissolved in alcohol or alcohol-water mixture In, the transistion metal compound solution that concentration is 0.01-100g/L is obtained, under agitation by above-mentioned solution and alkali metal or alkaline earth Alcoholic solution or the aqueous solution or the alcohol solution mixing of the hydroxide of metal, add MDC1 obtained by step 1), blended, stirring Or after being ultrasonically treated, heated in reducing atmosphere or inert atmosphere in 313-600K, separate and collect the solid in system, obtain The nano-complex.
32. according to the method for claim 31, it is characterised in that：In the step 1), the concentration of the solution of melamine For 1 × 10-3~102G/L, solvent are selected from water and can dissolve at least one of organic compound of melamine；
The mass ratio of the carbon material and melamine is 1：2~100：1；
The method for removing solvent is evaporation, centrifuges, filters or dry；
In the heat treatment step, atmosphere is inert atmosphere or oxygenous mixed-gas atmosphere；The temperature of heat treatment is 573- 973K；
In the step 2), the alcohol be C1-C8 monohydric alcohol, C1-C8 dihydric alcohol, C1-C8 dihydric alcohol derivative, At least one of C1-C8 trihydroxylic alcohol and the C1-C8 derivative of trihydroxylic alcohol；
The derivative of the dihydric alcohol of the C1-C8 is the unitary methoxy or ethoxy derivative of C1-C8 dihydric alcohol；
The derivative of the trihydroxylic alcohol of the C1-C8 is the unitary methoxy or ethoxy derivative of C1-C8 trihydroxylic alcohol；
In the alcohol-water mixture, the volumn concentration of water is 0-70%；
The reducing atmosphere is the atmosphere containing hydrogen.
33. according to the method for claim 32, it is characterised in that：In the alcohol-water mixture, the volumn concentration of water It is 0-50%.
34. according to the method for claim 31, it is characterised in that：Methods described also comprises the following steps：
The carbon material of the melamine derivative modification is substituted with nano-complex described in claim 2, and presses the step 2) the step of, is synthesized.
35. a kind of method for preparing nano-complex described in claim 2, comprises the following steps：
The acid or soluble-salt of any transition metal of at least one claim 1-4 are dissolved in alcohol or alcohol-water mixture In, the transistion metal compound solution that concentration is 0.01-100g/L is obtained, under agitation by it with alkali metal or alkaline-earth metal Alcoholic solution or the aqueous solution or the alcohol solution mixing of hydroxide, according still further to proportioning by gained liquid and at least one claim After any melamine condensation polymers of 1-14 and carbon material are mixed, stirred or be ultrasonically treated, in reducing atmosphere or lazy Property atmosphere in 313-600K heat, separate and collect the solid in system, obtain the nano-complex.
36. according to the method for claim 35, it is characterised in that：The alcohol is C1-C8 monohydric alcohol, the two of C1-C8 First alcohol, the C1-C8 derivative of dihydric alcohol, C1-C8 trihydroxylic alcohol and C1-C8 at least one of the derivative of trihydroxylic alcohol；
The derivative of the dihydric alcohol of the C1-C8 is the unitary methoxy or ethoxy derivative of C1-C8 dihydric alcohol；
The derivative of the trihydroxylic alcohol of the C1-C8 is the unitary methoxy or ethoxy derivative of C1-C8 trihydroxylic alcohol；
In the alcohol-water mixture, the volumn concentration of water is 0-50%；
The reducing atmosphere is the atmosphere containing hydrogen；
The mass ratio of the carbon material and melamine condensation polymer is 100：1-100；The mass ratio of the carbon material and metal is 10：0.01-90.
37. a kind of method for preparing nano-complex described in claim 2, comprises the following steps：
1) a kind of and any carbon materials of at least one claim 3-9 in melamine and cyanuric acid are uniformly mixed Close, then the another kind in melamine and cyanuric acid is uniformly mixed with said mixture；Above-mentioned suspension is subjected to hot place Reason, the carbon material MDC2 of melamine and cyanuric acid Derivatives Modified is obtained after being cooled to room temperature；
2) metallic colloid is prepared：By the soluble-salt of any transition metal of at least one claim 1-4 or containing the mistake The acid for crossing metal is dissolved in alcohol or alcohol-water mixture, is configured to the transistion metal compound solution that concentration is 0.01-100g/L, Then the alcoholic solution or the aqueous solution or alcohol solution of the hydroxide of alkali metal or alkaline-earth metal are added, gained mixed liquor is existed 343-533K is heated, and obtains the transition metal nano-cluster or alloy nanocluster colloidal solution；
3) MDC2 obtained by step 1) is added into water-miscible organic solvent or its in the mixed solvent with water, is ultrasonically treated system Obtain suspension；Colloidal transition metal solution obtained by step 2) and above-mentioned suspension are pressed into transition metal：MDC2 mass ratioes are 1： 0.001-9 ratio mixing, stirring or supersound process, isolate precipitation and by it under 273-673K, in inert atmosphere or also Handled in Primordial Qi atmosphere or under reduced pressure, obtain the nano-complex.
38. according to the method for claim 37, it is characterised in that：In the step 1), the method for the mixing is by three A kind of solution in poly cyanamid and cyanuric acid uniformly mixes with the carbon material, using volatilization, centrifugation, evaporation, mistake Filtering method removes the solvent in the mixture, by another solution in gained mixture and melamine and cyanuric acid Uniformly mixing, the solvent in the mixture is removed using volatilization, evaporation, filter method；The mixing, remove at solvent or heat The temperature for managing step is 273-573K；The atmosphere of the heat treatment process is inert atmosphere or oxygenous mixed gas；
The mass ratio of the melamine and cyanuric acid is 10:1~1：2；Melamine and the cyanuric acid solution it is dense Spend for 0.1~102g/L；The solvent of the solution is included in water and the organic compound that can dissolve melamine and cyanuric acid At least one；The organic compound includes alcohols, ketone, esters and ether compound or its mixture；In addition, in the step Product can also be washed, cleaning solvent includes water or conventional organic solvent, including alcohol, nitrile, ketone solvent；The mixed solvent The volumn concentration of reclaimed water is 0-90%；
In the step 2), the alcohol be C1-C8 monohydric alcohol, C1-C8 dihydric alcohol, C1-C8 dihydric alcohol derivative, At least one of C1-C8 trihydroxylic alcohol and the C1-C8 derivative of trihydroxylic alcohol；
The derivative of the dihydric alcohol of the C1-C8 is the unitary methoxy or ethoxy derivative of C1-C8 dihydric alcohol；It is described The derivative of C1-C8 trihydroxylic alcohol is the unitary methoxy or ethoxy derivative of C1-C8 trihydroxylic alcohol；
In the alcohol-water mixture, the volumn concentration of water is 0-50%；
The precipitation of isolating includes being separated in a manner of filtering or centrifuge.
39. the method according to claim 31 or 37, it is characterised in that：Methods described also comprises the following steps：
The carbon material of the melamine derivative modification is substituted with nano-complex described in claim 2, and presses claim Step 3) described in 31 steps 2) or claim 37 is synthesized.
40. according to the method described in claim 31,34,35 or 37, it is characterised in that：Methods described also includes following step Suddenly：
Cupric obtained by claim 31,34,35 or 37 methods describeds and/or the nano-complex of the alloy nanocluster of nickel are entered Row chemical attack is to remove the light transition metal in part；
The chemical attack is to use acid treatment；
The acid includes at least one of nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid.
41. application of any nano-complexes of claim 1-30 as electrochemical catalyst.
42. application according to claim 41, it is characterised in that：Any nano-complex conducts of claim 1-30 The application of the catalyst of fuel cell reaction；
The fuel cell reaction is oxygen reduction reaction or methanol oxidation.
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CN103515627B (en) * 2012-06-19 2016-02-10 北京大学 A kind of aza carbon nanohorn-graphite nanometer composite material and preparation method thereof and application
CN102916203B (en) * 2012-11-07 2014-10-01 武汉理工大学 Cathode non-platinum catalyst of proton exchange membrane fuel cell and preparation method thereof

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