CN105312087A - Nano-grade composite catalyst, and preparation method and application thereof - Google Patents

Nano-grade composite catalyst, and preparation method and application thereof Download PDF

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CN105312087A
CN105312087A CN201410366195.1A CN201410366195A CN105312087A CN 105312087 A CN105312087 A CN 105312087A CN 201410366195 A CN201410366195 A CN 201410366195A CN 105312087 A CN105312087 A CN 105312087A
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nano
melamine
derivative
alcohol
solution
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CN105312087B (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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    • Y02E60/50—Fuel cells

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Abstract

The invention discloses a nano-grade composition, a preparation method thereof, and an application thereof as an electrochemical catalyst. The nano-grade composition provided by the invention is basically composed of a melamine derivative, a carbon material, and transition metal or transition metal alloy nano-cluster. The carbon material comprises at least one selected from conductive carbon black, activated carbon, carbon nano-horn, N-doped carbon nano-horn, carbon nano-tube, graphene, graphite and carbon fiber material. The metal nano-cluster is at least one selected from Pt, Ru, Pd, Rh and Ir nano-clusters. The alloy nano-cluster is nano-cluster formed by more than two elements selected from Pt, Ru, Pd, Rh, Ir, Fe, Cu and Ni. The mass percentage content of the transition metal or alloy nano-cluster is 0.1-90%. The size of the transition metal or alloy nano-cluster is 0.5-10nm. As a fuel cell catalyst, the nano-grade composition provided by the invention has excellent electrocatalytic activity upon reactions such as oxygen reduction and methanol oxidation.

Description

Nano-composite catalyst and preparation method thereof and application
Technical field
The present invention relates to a kind of nano-composite catalyst and preparation method thereof and application.
Background technology
Transition metal and alloy nanocluster thereof are the nano materials that a class has significant application value; can be used for development several functions materials and devices (Y.Wang; Y.Wei; " MetalNanoclusters " (Chapter) inH.S.Nalwa; Ed.; EncyclopediaofNanoscienceandNanotechnology; Vol.5; 337-367; 2004AmericanScientificPublishers), in catalysis, Conversion of Energy; there is application prospect very widely the aspects such as environmental protection (vent gas treatment, purification of air etc.).Inventor had once invented a class " non-protected type " noble metal and alloy nanocluster thereof and manufacture method thereof, this kind of metal nanometre cluster is only by simple ion and organic solvent molecule used as stabilizers, not only size is little, narrow diameter distribution, can synthesize in enormous quantities, and by adding acidic aqueous solution, can easily it be separated with the form of precipitation and carry out purifying from dispersion, metal nanometre cluster precipitation again can be scattered in many solvents and form stable colloidal solution (Y.Wang, J.Ren, K.Deng, L.Gui, Y.Tang, Chem.Mater.2000, 12, 1622, Chinese invention patent, ZL99100052.8), this type of metal nanometre cluster has been used to synthetic fuel cell catalyst electrode (MaoS., MaoG., Supportednanoparticlecatalyst.USAPatent, US2003/0104936, ZhouW., etal., App.Catal.B.2003,46,273).
The noble-metal nanoclusters such as Pt, Ru play very important effect in fields such as chemical industry, petroleum refinement, petrochemistry, medicine, environmental protection and the energy.Due to the scarcity of resources of the noble metals such as Pt, Ru, expensive, by the noble-metal nanoclusters such as light transition metal and Pt, Ru are formed binary or multicomponent alloy, can reduce the consumption of noble metal, alloy has the specific function not available for single metal simultaneously.On the other hand, by metal and alloy nanocluster thereof and different carriers compound tense, the interaction between the physicochemical properties of carrier surface and metal/carrier also can play significant impact to catalytic performance.
The electrode catalyst used in current Proton Exchange Membrane Fuel Cells (PEMFC) is mainly the supporting platinum-based metal catalyst of carbon (Pt/C).One of subject matter existed in PEMFC practicalization is the activation polarization problem of Pt/C catalyst, and the electrode reaction speed of the reaction such as methanol oxidation and hydrogen reduction urgently improves further; There are some researches show, some the platinum base alloy catalyst (PtM/C) prepared by the method for alloying has higher catalytic activity and anti-poisoning capability compared with Pt/C catalyst.
Metal and alloy nanocluster thereof are carried on carbon carrier, usually can adopt the method such as infusion process, reduction sedimentation, the absorption of protection metallic colloid, Coordination Capture, deposition, embedding.Metal-carbon composite prepared by distinct methods has different microstructures, and as different compositions, different particle sizes and domain size distribution etc., these can make a significant impact the performance of metal-carbon composite.There are some researches show, the average grain diameter of Pt metal nanometre cluster is the mass activity (K.Kinoshita, J.Electrochem.Soc.1990,137,845) that the Pt/C catalyst of 3-5 nanometer is very high to the performance of PEMFC Cathodic oxygen reduction.Prior art discloses the bimetallic catalysts such as multiple carbon Supported Pt Nanoparticles-copper, the carbon wherein with the initial platinum/copper atom ratio of 1:3 carries the reduction reaction of catalyst to oxygen that platinum/copper bimetallic catalyst prepared after electrochemical corrosion and shows higher electro catalytic activity.Strasser etc. adopt the method for dipping-high temperature reduction to prepare carbon and carry Pt-Cu electrochemical catalyst, and they are by Pt/C catalyst and Cu (NO 3) 2after water solution mixture freeze drying, in high temperature (600,800,950 DEG C), 4%H 2reduce under atmosphere.When alloying temperature is low (600-800 DEG C), catalyst alloyization is incomplete, has simple substance Cu to exist, cannot obtain optimized platinum/copper ratio.And when alloying temperature height (as 950 DEG C), metallic is assembled, grow up, have a strong impact on catalytic activity.The method be difficult to realize the composition of metal nanometre cluster and particle diameter simultaneously controlled, prepared catalytic performance still has much room for improvement (S.KohandP.Strasser, J.Am.Chem.Soc.2007,129,12624).
At present, one of subject matter existed in carbon load alloy fuel cell catalyst be how to prepare alloy particle size little (being less than 5 nanometers), metal forms controllable electrochemical catalyst.In fuel cell catalyst, tenor very high (usual 10-50%), makes the solution of the problems referred to above have very large challenge.
On the other hand, interaction between carrier and metal has remarkable impact to catalyst catalytic performance, usually the high-specific surface area material with carbon element that electric conductivity is good is used in fuel-cell catalyst, to obtain larger metal ladings and metal dispersity (E.Antolini, AppliedCatalysisB:Environmental2009,88,1).But common conductive carbon black, the materials such as CNT, graphite are rare are strong to the metal nanometre cluster adsorption capacity in colloidal solution, easily cause noble-metal-supported efficiency in the supported process of metallic colloid low, and metal ladings is on the low side and the problems such as easy generation reunion.
Summary of the invention
The object of this invention is to provide a kind of nano-complex Catalysts and its preparation method and application.
Nano-complex provided by the invention, comprises melamine derivative (MD), material with carbon element and nano-cluster; Wherein, the material forming described nano-cluster is transition metal or transition metal alloy;
The quality of described nano-cluster accounts for the 0.1-90% of described nano-complex gross mass;
The mass ratio of described material with carbon element and melamine derivative is 1:1-100:1.
Above-mentioned nano-complex also can only be made up of said components.
Described transition metal is selected from least one of Pt, Ru, Pd, Rh and Ir; Transition metal in described transition metal alloy is selected from least two kinds in Pt, Ru, Pd, Au, Rh, Ir, Cu and Ni.
The particle diameter of the described nano-cluster recorded by electron microscope is 0.5 to 10 nanometer, specifically can be 0.5-2 nanometer; 0.5-5 nanometer, 0.5-10 nanometer, 1-5 nanometer;
The quality of described nano-cluster accounts for the 1-90% of described nano-complex gross mass, specifically can be 0.1%, 1%, 3%, 10%, 16%, 19.2%, 20%, 27%, 27.8%, 28.9%, 30%, 40%, 41%, 50%, 59%, 60%, 80%, 85%, 0.1-27%, 0.1-40%, 0.1-60%, 0.1-80% or 3-85%;
The mass ratio of described material with carbon element and melamine derivative is 5-30:1, specifically can be 1-30:1,1-50:1,3-99:1;
Described melamine derivative is selected from least one in the derivative that melamine condensation polymer and melamine and cyanuric acid formed.
In above-mentioned nano-complex, described melamine derivative (MD) comprises at least one in the derivative that melamine condensation polymer and melamine and cyanuric acid formed.
The N1s electron binding energy of the x-ray photoelectron spectroscopy (XPS) of described melamine condensation polymer is mainly distributed in 397 ~ 402eV scope, and in described XPS spectrum, N1s peak comprises graphite N, skeleton N (-C=N-C) ,-NH 2graphite N and amido (-NH is comprised with the signal of amide groups 2) N1s electron binding energy.
Described melamine condensation polymer obtains according to the method preparation comprised the steps: by melamine polycondensation in a heated condition; In described heating condition, temperature is specially 573-973K.
Described melamine condensation polymer is selected from least one in melem and melem condensation polymer;
The derivative that described melamine and cyanuric acid are formed comprises the compound that melamine and cyanuric acid are formed;
The product that the derivative that described melamine and cyanuric acid the are formed method comprised in accordance with the following steps is prepared and obtained: melamine and cyanuric acid are mixed with material with carbon element and heats; The temperature of described heating is 278-573K.
The derivative that described melamine and cyanuric acid are formed comprises the bond complexes that melamine and cyanuric acid are formed.
Described melamine derivative adsorbs or is chemically bound in carbon material surface and/or metal nanometre cluster surface.
Described melamine derivative can adsorb or be chemically bound in the material with carbon element (MDC) that carbon material surface forms melamine derivative modification, and the specific area of the material with carbon element (MDC) that described melamine derivative is modified is 40-1300m 2/ g, is specially 50-550m 2/ g, 100-1300m 2/ g, nitrogen content is 0.1-30wt%, is preferably 1-30wt%;
The material with carbon element that described melamine derivative is modified comprises the material with carbon element that melamine condensation polymer is modified, and its N1s electron binding energy recorded by x-ray photoelectron spectroscopy (XPS) is mainly distributed in 397 ~ 402eV scope;
The material with carbon element that described melamine derivative is modified also comprises the material with carbon element that compound that melamine and cyanuric acid formed is modified, and its N1s electron binding energy recorded by x-ray photoelectron spectroscopy (XPS) is mainly distributed in 397 ~ 403eV scope.
The specific area of described material with carbon element is 40-2000m 2/ g, specifically can be 60-1500m 2/ g, 100-1500m 2/ g.
Described material with carbon element is selected from least one in conductive carbon black, active carbon, N-doping carbon nanohorn, carbon nanohorn, CNT, Graphene, mesoporous carbon, graphite and carbon fibre material;
Nano-complex provided by the invention comprises the compound with following feature: its N1s electron binding energy recorded by x-ray photoelectron spectroscopy (XPS) is mainly distributed in 397 ~ 402eV scope.
The method of the described nano-complex of preparation provided by the invention, is also method one, comprises the steps:
1) solution of melamine is mixed with aforementioned material with carbon element, heat-treat after removing solvent, be cooled to room temperature, obtain the material with carbon element MDC1 that melamine condensation polymer is modified;
2) acid of foregoing transition metal or soluble-salt are dissolved in alcohol or alcohol-water mixture, obtain the transistion metal compound solution that concentration is 0.01-100g/L, under agitation by the alcoholic solution of the hydroxide of above-mentioned solution and alkali metal or alkaline-earth metal or the aqueous solution or alcohol water mixed solution, add step 1 again) MDC1 for preparing, after mixing, stirring or ultrasonic process, heat in 313-600K in reducing atmosphere or inert atmosphere, solid in separated and collected system, obtains described nano-complex.
The step 1 of said method) in, the concentration of melamine solution is 1 × 10 -3~ 10 2g/L, solvent is selected from water and can dissolves at least one in the organic compound of melamine; Specifically can be selected from compound or its mixtures such as water, alcohols, ketone, ester class and ethers;
The mass ratio of described material with carbon element and melamine is 1:2 ~ 100:1, is specially 1:2 ~ 40:1:1:1 ~ 9:1
The method of described removal solvent is evaporation, centrifugation, filtration or drying;
In described heat treatment step, atmosphere is inert atmosphere or oxygenous mist; Heat treated temperature is 573-973K;
In addition, in described step 1) be cooled to room temperature step after, in step 2) before, also can wash products therefrom, cleaning solvent comprises water or conventional organic solvent, comprises alcohol, nitrile, ketone equal solvent.
Described step 2) in, described alcohol is at least one in the derivative of the trihydroxylic alcohol of the monohydric alcohol of C1-C8, the dihydroxylic alcohols of C1-C8, the derivative of the dihydroxylic alcohols of C1-C8, the trihydroxylic alcohol of C1-C8 and C1-C8;
Wherein, the derivative of the dihydroxylic alcohols of described C1-C8 is specially the unitary methoxy or ethoxy derivative of the dihydroxylic alcohols of C1-C8;
The derivative of the trihydroxylic alcohol of described C1-C8 is specially the unitary methoxy or ethoxy derivative of the trihydroxylic alcohol of C1-C8;
In described alcohol-water mixture, the volumn concentration of water is 0-70%; Specifically can be 0-50%.
Described reducing atmosphere is the atmosphere containing hydrogen.
In addition, in described step 2) in, in reducing atmosphere or inert atmosphere after 313-600K heating steps, before the solid in separated and collected system, for the ease of the separation of product, also can add in gained mixture acid solution make pH be less than 7 and by mixture stir, leave standstill process.
Described method also comprises the steps:
The material with carbon element that described melamine derivative modifies is substituted with described nano-complex, and by the described step 2 of the method) synthesize.
Present invention also offers a kind of method preparing described nano-complex, be also method two, comprise the steps:
The acid of foregoing transition metal or soluble-salt are dissolved in alcohol or alcohol-water mixture, obtain the transistion metal compound solution that concentration is 0.01-100g/L, under agitation by its with alkali metal or the alcoholic solution of the hydroxide of alkaline-earth metal or the aqueous solution or alcohol solution mix, gained liquid and the condensation polymer of melamine described in this description and material with carbon element carried out mix according to proportioning again, to stir or after ultrasonic process, heat in 313-600K in reducing atmosphere or inert atmosphere, solid in separated and collected system, obtains described nano-complex.
In said method, described alcohol is at least one in the derivative of the trihydroxylic alcohol of the monohydric alcohol of C1-C8, the dihydroxylic alcohols of C1-C8, the derivative of the dihydroxylic alcohols of C1-C8, the trihydroxylic alcohol of C1-C8 and C1-C8;
Wherein, the derivative of the dihydroxylic alcohols of described C1-C8 is specially the unitary methoxy or ethoxy derivative of the dihydroxylic alcohols of C1-C8;
The derivative of the trihydroxylic alcohol of described C1-C8 is specially the unitary methoxy or ethoxy derivative of the trihydroxylic alcohol of C1-C8;
In described alcohol-water mixture, the volumn concentration of water is 0-70%, specifically can be 0-50%.
Described reducing atmosphere is the atmosphere containing hydrogen.
The mass ratio of described material with carbon element and melamine condensation polymer is 100:1-100; The mass ratio of described material with carbon element and metal is 10:0.01-90.
The derivative that described melamine and cyanuric acid are formed is the bond complexes that melamine and cyanuric acid are formed.
The N1s electron binding energy of the x-ray photoelectron spectroscopy of described nano-complex is mainly distributed in 397 ~ 403eV scope.
In addition, in reducing atmosphere or inert atmosphere after 300-600K heating steps, before the solid in separated and collected system, for the ease of the separation of product, also can add in gained mixture acid solution make pH be less than 7 and by mixture stir, leave standstill process.
Described melamine condensation polymer comprises the product prepared as follows: make melamine polycondensation in a heated condition; In described heating condition, temperature is 573-973K.
Present invention also offers a kind of method preparing described nano-complex, be also method three, comprise the steps:
1) by the one in melamine and cyanuric acid and aforementioned material with carbon element Homogeneous phase mixing, then by the another kind in melamine and cyanuric acid and said mixture Homogeneous phase mixing; Above-mentioned suspension is heat-treated, after being cooled to room temperature, obtains the material with carbon element (MDC2) of melamine and cyanuric acid Derivatives Modified;
2) prepare metallic colloid: by the soluble-salt of foregoing transition metal or containing the acid dissolve of described transition metal in alcohol or alcohol-water mixture, be mixed with the transistion metal compound solution that concentration is 0.01-100g/L, then the alcoholic solution of the hydroxide of alkali metal or alkaline-earth metal or the aqueous solution or alcohol solution is added, by gained mixed liquor in 343-533K heating, obtain transition metal nano-cluster colloidal solution;
3) by step 1) gained MDC2 adds can in the mixed solvent of the organic solvent miscible with water or itself and water, and ultrasonic or dispersed with stirring obtains suspension; By step 2) gained transition metal nano-cluster colloidal solution and above-mentioned suspension be in transition metal: MDC2 mass ratio is the ratio mixing of 1:0.001-9, stir or ultrasonic process, isolate precipitation and by it under 273-673K, process in inert atmosphere or reducing atmosphere or under reduced pressure, obtain described nano-complex.
The step 1 of said method) in, the method of described mixing comprises a kind of solution in melamine and cyanuric acid and described material with carbon element Homogeneous phase mixing, adopt the methods such as volatilization, evaporation, filtration by the solvent removing in this mixture, gained mixture is mixed with the alternative dissolution homogeneity in melamine and cyanuric acid, adopts the methods such as volatilization, evaporation, filtration by the solvent removing in this mixture; Described mixing or except the temperature of desolventizing and heat treatment step be 273-573K; The atmosphere of described heat treatment process is inert atmosphere or oxygenous mist;
The mass ratio of described melamine and cyanuric acid is 10:1 to 1:2; The concentration of described melamine and cyanuric acid solution is 0.1 ~ 10 2g/L; The solvent of described solution comprises water and can dissolve at least one in the organic compound of melamine and cyanuric acid; Described organic compound comprises compound or its mixtures such as alcohols, ketone, ester class and ethers; In addition, also can wash product in this step, cleaning solvent comprises water or conventional organic solvent, comprises alcohol, nitrile, ketone equal solvent; In described mixed solvent, the volumn concentration of water is 0-90%;
Described step 2) in, described alcohol is at least one in the derivative of the trihydroxylic alcohol of the monohydric alcohol of C1-C8, the dihydroxylic alcohols of C1-C8, the derivative of the dihydroxylic alcohols of C1-C8, the trihydroxylic alcohol of C1-C8 and C1-C8; Wherein, the derivative of the dihydroxylic alcohols of described C1-C8 is specially the unitary methoxy or ethoxy derivative of the dihydroxylic alcohols of C1-C8; The derivative of the trihydroxylic alcohol of described C1-C8 is specially the unitary methoxy or ethoxy derivative of the trihydroxylic alcohol of C1-C8;
In described alcohol-water mixture, the volumn concentration of water is 0-70%, specifically can be 0-50%.
Described step 3) in, described in isolate precipitation and comprise filtering or centrifugal mode is separated.
Described method also comprises the steps:
The material with carbon element that described melamine derivative modifies is substituted with described nano-complex, and by the described step 3 of the method) synthesize.
In addition, in three kinds of preparation methods of the present invention, substitute the material with carbon element of described melamine derivative modification with nano-complex prepared by the present invention, and also belong to protection scope of the present invention by the product that described step is synthesized; This synthetic method formed of replacing also belongs to protection scope of the present invention.
Nano-complex of the present invention also comprise to the nano-complex of the alloy nanocluster of above-mentioned three kinds of method gained cuprics and/or nickel carry out chemical attack with the light transition metal of remove portion obtained product.
Described chemical attack comprises with acid treatment, and described acid is at least one in nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid.
Material with carbon element (i.e. MDC1 and MDC2) that the present invention also provides a kind of melamine derivative to modify and preparation method thereof.
In addition, the fuel cell electrochemical catalyst being active ingredient with above-mentioned nano-complex provided by the invention and this nano-complex, preparing the application in fuel cell electrochemical catalyst, also belong to protection scope of the present invention.Wherein, described fuel cell comprises hydrogen reduction fuel cell or methanol oxidation fuel cells.
Melamine is the heterocyclic compound that a class has extensive use, under heating state, a series of polycondensation reaction can be there is in melamine, produce the product (L.CostaandG.Camino such as close white amine, Miller amine, Miller amine condensation polymer and C3N4, J.Therm.Anal., 1988,34,423).Melamine and cyanuric acid effect easily form the compound being insoluble in water, there is in compound abundant hydrogen bond network and nano aperture (KlausHuthmacher, DieterMost " CyanuricAcidandCyanuricChloride " Ullmann'sEncyclopediaofIndustrialChemistry " 2005; Wiley-VCH, Weinheim.ISBN10.1002/14356007.a08191).The present invention proposes to utilize melamine derivative, the i.e. modified carbon material surface such as compound of melamine condensation polymer, melamine and cyanuric acid, by the interaction of metal nanometre cluster and melamine derivative, supported being easy to of metal nanometre cluster colloidal particle is carried out, suppress nano particle agglomeration, improve the catalytic performance of catalyst.We find simultaneously, and in prepared compound, exist and act synergistically between melamine derivative and platinum group metal nano-cluster, this makes it significantly improve the intrinsic catalytic activity of oxygen reduction reaction.
Prepare metal particle diameter little, narrowly distributing, and alloy forming controlled high carrying capacity noble metal fuel cell catalyst to the activity improving catalyst, increases chemical energy-electric energy conversion efficiency significant, is also that people attempt a difficult problem for solution for a long time.The affecting laws of cooperative effect to catalytic performance of fuel-cell catalyst carrier and metallic it be unclear that, before making the present invention, the compound that the material with carbon element not having example to show to be modified by melamine derivative or melamine derivative and metal nanometre cluster are formed has excellent electrocatalytic oxidation reducing property or electro-catalysis methanol oxidation performance.
The present invention utilizes the interaction of developed carrier (melamine derivative modified carbon material) and described metal and alloy particle, effectively inhibit the agglomeration of metal or alloy particle in catalyst, even if the particle diameter of metal and alloy also can be made and form controlled under high metal ladings, to obtain in catalyst metal and alloy nano particle particle diameter is little, narrowly distributing, overcome in the past in high carrying capacity fuel battery metal and alloy catalyst metal nanoparticle size large, a difficult problem for composition skewness.
The research of the present inventor shows, develop in catalyst, electro transfer effect and/or synergic catalytic effect is there is between metal and described melamine derivative, by the interaction between this type of special carrier and metal and cooperative effect, the fuel cell reactions such as institute's invention catalyst towards oxygen reduction or methanol oxidation show excellent catalyst activity, and this simply cannot know by inference from knowledge in the past.
Such as, the nano-complex catalyst (Pt-Cu/MDC1-1) containing Pt-Cu alloy nanocluster prepared by embodiment 1 is 4 times of commercial Pt/C-JM catalyst (Pt content 9.4wt%) to the mass activity of oxygen reduction reaction (the dynamics current value at 0.9Vvs.RHE place as evaluation index, 720A/gPt); (the dynamics current value at 0.95Vvs.RHE place is as evaluation index to the mass activity of oxygen reduction reaction for Pt-Cu alloy nanocluster nano-complex catalyst (Pt-Cu/MDC1-3) prepared by embodiment 3,374A/gPt) be commercial Pt/C-JM catalyst (46A/gPt, Pt content 52wt%) 8 times, its mass activity is much better than the carbon in the past reported and carries PtCu catalyst; The catalytic activity (0.55Vvs.RHE) of PtRu alloy nanocluster nano-complex catalyst Pt Ru/MDC1-4 to methanol oxidation prepared by embodiment 4 is 2.6 times of commercial PtRu/C-JM catalysis electrode.The mass activity (the dynamics current value at 0.9Vvs.RHE place be 364A/gPt) of Pt metal nanometre cluster complex catalyst (Pt/MDC2-1) prepared by embodiment 14 to oxygen reduction reaction is 2 times of commercial Pt/C-JM catalysis electrode (167A/gPt), and gained mass activity carries the peak of Pt catalyst far above the carbon reported before.But, the electrochemical surface area of Pt/MDC2-1 is but low than described commercial catalyst by 62%, visible part Pt surface cover by melamine derivative, and the two sp act center formed has excellent latent active (specificactivity), thus make to be greatly improved to the vital catalyst mass activity of practical application.
Accompanying drawing explanation
The x-ray photoelectron spectroscopy (N1s) of melamine condensation polymer MD1 (b) that Fig. 1 is raw material melamine (a), prepared by comparative example 1 and material with carbon element MDC1-1 (c) that melamine condensation polymer prepared by embodiment 1 is modified.Graphite C 1s combines can 284.5eV.
The powder x-ray diffraction spectrum of the Pt-Cu alloy nanocluster complex catalyst Pt-Cu/MDC1-1 that Fig. 2 (a) is prepared for embodiment 1, Cu target K α; B x-ray photoelectron spectroscopy (N1s) that () is Pt-Cu/MDC1-1, graphite C 1s combines can 284.5eV.
Fig. 3 is the electromicroscopic photograph of Pt-Cu alloy nanocluster complex catalyst Pt-Cu/MDC1-1 prepared by embodiment 1.
Fig. 4 is Pt-Cu alloy nanocluster complex catalyst Pt-Cu/MDC1-1 prepared by embodiment 1 and the catalytic activity being purchased redox reactions on Pt/C-JM catalyst.
Fig. 5 be embodiment 3 prepare the electromicroscopic photograph of Pt-Cu alloy nanocluster complex catalyst Pt-Cu/MDC1-3.
Fig. 6 is Pt-Cu alloy nanocluster complex catalyst Pt-Cu/MDC1-3 prepared by embodiment 3 and the catalytic activity being purchased redox reactions on Pt/C-JM catalyst.
Fig. 7 is the XPS spectrum of the N1s of material with carbon element MDC2-1 and Pt/MDC2-1 of the Derivatives Modified that melamine and cyanuric acid prepared by embodiment 14 are formed, graphite C 1s combination energy 284.5eV.
Fig. 8 is the electromicroscopic photograph of Pt metal nanometre cluster complex catalyst (Pt/MDC2-1) prepared by embodiment 14.
Fig. 9 is the cyclic voltammetry curve of Pt metal nanometre cluster complex catalyst (Pt/MDC2-1) in a nitrogen atmosphere in high chloro acid solution (0.1M) prepared by embodiment 14.
Figure 10 is the electromicroscopic photograph of Pt metal nanometre cluster complex catalyst (Pt/MDC2-2) prepared by embodiment 15.
The melamine that Figure 11 is raw material cyanuric acid CA (a), prepared by melamine (b), embodiment 15 and material with carbon element MDC2-2 (c) of Derivatives Modified that cyanuric acid is formed are composed with the N1sXPS of Pt metal nanometre cluster complex catalyst Pt/MDC2-2 (d), and graphite C 1s combines can 284.5eV.
Figure 12 is the infrared absorption spectroscopy of melamine condensation polymer MD1 prepared by comparative example 1.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is conventional method if no special instructions.Described raw material all can obtain from open commercial sources if no special instructions.
Embodiment 1, prepare the Pt-Cu alloy nanocluster complex catalyst Pt-Cu/MDC1-1 (method one) that tenor is 16wt%
By 0.1g melamine goes in 100mL water, make melamine solution.Conductive carbon black (is purchased xC-72R, 0.4g, specific area 254m 2/ g) add in above-mentioned melamine solution, ultrasonic process 20 minutes, in 150 DEG C of oil baths heating boil off aqueous solvent, obtain melamine-material with carbon element ( xC-72R) mixture.In air atmosphere, mixture is heated to 613K in Muffle furnace, be cooled to room temperature after insulation 1h, obtain the material with carbon element MDC1-1 that melamine condensation polymer is modified, elementary analysis shows that in MDC1-1, nitrogen content is 4.4%.BET specific surface area test shows that the specific area of MDC1-1 is 100m 2/ g.
The N1sXPS spectrum of raw material melamine Melamine (a), melamine condensation polymer MD-1 (b) of comparative example 1 preparation and material with carbon element MDC1-1 (c) of melamine condensation polymer modification is compared in accompanying drawing 1.In melamine XPS spectrum, N1s electron binding energy is mainly distributed in 396.5-401eV scope, is skeleton N (-C=N-C) and terminal amido (-NH 2) signal of nitrogen containing species; And the N1s electron binding energy of MD-1 and MDC1-1 is mainly distributed in 396-402eV scope.Compare with MD-1, MDC1-1XPS spectrum has an acromion at 399.8eV place, its combination can compared with the high 0.6eV of combination energy of terminal amido in MD-1, combining with N1s in amido link can be consistent, show that the terminal amido of intermediate product MD-1 and the carboxyl on VulcanXC-72R surface of formation in MDC1-1 synthesis there occurs condensation reaction, form amido link.
By 31.1mg six hydration chloroplatinic acid and 26.5mg hydration Schweinfurt green Cu (CH 3cOO) 2h 2o is dissolved in 50ml ethylene glycol, with the ethylene glycol solution (0.25mol/L) of NaOH, the pH value of above-mentioned solution is adjusted to 10, under agitation being joined by gained mixed liquor is dispersed with in the 80ml ethylene glycol of 86.5mgMDC1-1, at room temperature continue stirring 5 minutes, by gained reactant in a nitrogen atmosphere, add hot reflux in 573K and be cooled to room temperature after 4 hours.Mixture is filtered, with water and ethanol washing solid sediment.By gained solid sediment vacuum drying 4h under 343K, i.e. obtained Pt-Cu alloy nanocluster complex catalyst Pt-Cu/MDC1-1.
Accompanying drawing 2a is the X-ray diffraction spectrum of Pt-Cu/MDC1-1 catalyst, wherein 42.1 °, 48.5 °, the signals assignment of 71.8 ° and 86.9 ° (111) of face-centred cubic structure Pt/Cu alloy nano particle (Pt/Cu atomic ratio is 29:71) in catalyst, (200) diffraction maximum that, (220) and (311) crystal face is corresponding.There is no the signal of simple substance Pt and Cu in spectrogram, show that alloying is complete.
Fig. 2 b is that Pt-Cu/MDC1-1 catalyst n 1sXPS composes, and its N1s electron binding energy is mainly distributed in 397 ~ 402eV scope.
Transmission electron microscope (TEM) photo of Pt-Cu/MDC1-1 catalyst as shown in Figure 3.In Pt-Cu/MDC1-1 catalyst, metal nanoparticle is scattered on carrier well, and its average grain diameter is 3.8 nanometers, and domain size distribution is 1.5-8.5 nanometer.Inductively coupled plasma atomic emission (ICP-AES) test analysis shows, Pt and Cu total metal content is 16wt%, Pt content is 9.1wt%.
The preparation of catalysis electrode: take prepared Pt-Cu/MDC1-1 catalyst fines 10mg, ultrasonic process in 5mL absolute ethyl alcohol, add 100 μ L in above-mentioned dispersion solution, continues ultrasonic process 20 minutes.The suspension drawing 20 μ L catalyst with liquid-transfering gun is added drop-wise to glassy carbon electrode surface, under room temperature dry 0.5 hour in atmosphere, then vacuum drying 1 hour under 393K, i.e. obtained Pt-Cu/MDC1-1 catalysis electrode.This electrode is placed in perchloric acid (0.1M), carries out cyclic voltammetry scan activation process in 0.05-1.2V (vsRHE) electromotive force interval.
Record in the perchloric acid solution (0.1M) that oxygen is saturated, the mass activity of the catalyst oxygen reduction reaction after above-mentioned activation process is comparatively purchased Pt/C-JM (purchased from JohnsonMatthey company, platinum content: 9.4wt%) catalyst mass activity under the same conditions high 4 times (table one, Fig. 4).In table one, dynamics current value is according to Koutecky-Levich formulae discovery, and 0.9V data take from polarization curves of oxygen reduction.
Table one, Pt-Cu/MDC1-1 and be purchased Pt/C-JM catalyst towards oxygen reduction reaction catalytic activity contrast
Test condition: temperature: 303K, the perchloric acid solution (0.1M) that oxygen is saturated, sweep speed: 5mV/s.
Embodiment 2, prepare the Pt-Cu alloy nanocluster complex catalyst Pt-Cu/MDC1-2 that tenor is 41wt%
(method one)
The material with carbon element MDC1-1 of melamine condensation polymer modification is prepared by method described in embodiment 1.
1g six hydration chloroplatinic acid is dissolved in 50mL ethylene glycol for subsequent use.In 313K under agitation, 7.6mL six hydration chloroplatinic acid (0.31mmol) ethylene glycol solution is added in the ethylene glycol solution (227mL) being dissolved with 150mg mono-hydration Schweinfurt green, the ethylene glycol solution (0.25mol/L) of NaOH regulates the pH to 10 of above-mentioned solution, stirs 30 minutes.Above-mentioned mixed liquor dropped in the 324mL ethylene glycol solution being dispersed with MDC1-1 (350mg), in a nitrogen atmosphere, add hot reflux in 471K and be cooled to room temperature after 4 hours, filter, wash, in 343K vacuum drying 5 hours.Get above-mentioned solid product 350mg, be scattered in 324mL ethylene glycol, under agitation, add the chloroplatinic acid ethylene glycol solution that 12.93mL configures, prepare suspension A.Be dissolved in 365mL ethylene glycol solution by 242.1mg mono-hydration Schweinfurt green, preparation solution B, adds A by B, the ethylene glycol solution (0.25mol/L) of NaOH is dripped in gained mixture, regulate pH to 9, in a nitrogen atmosphere, add hot reflux in 471K and be cooled to room temperature after 4 hours.Mixture is filtered, with water and ethanol washing solid product.By the vacuum drying 4 hours under 343K of gained solid product, i.e. the obtained described complex catalyst Pt-Cu/MDC1-2 containing Pt-Cu alloy nanocluster.ICP-AES analyzes and shows, in Pt-Cu/MDC1-2, Pt/Cu atomic ratio is 31:69, Pt metal ladings is 24.1wt%, and average grain diameter is 3.1 nanometers.
Embodiment 3, prepare the Pt-Cu alloy nanocluster complex catalyst Pt-Cu/MDC1-3 that tenor is 27.8wt%
By Pt-Cu/MDC1-2 catalyst (50mg) ultrasonic disperse prepared by embodiment 2 in the nitric acid (20mL) of 1M, after 298K stirs 20 hours, centrifugation also washes precipitation with water to remove residual acid, gained solid product, in 298K vacuum drying 3 hours, obtains Pt-Cu alloy nanocluster complex catalyst Pt-Cu/MDC1-3.ICP-AES analyzes and shows, in Pt-Cu/MDC1-3, Pt/Cu atomic ratio is 72:28, Pt metal ladings is 24.7wt%.
The TEM photo of PtCu/MDC1-3 catalyst as shown in Figure 5.In Pt-Cu/MDC1-3, the average grain diameter of metal nanoparticle is 2.1 nanometers, and domain size distribution is 1.5-3.5 nanometer.
By the Pt-Cu/MDC1-3 catalyst prepared by characterizing method testing example 3 described in embodiment 1 and be purchased Pt/C-JM catalyst (platinum content: the 52wt%) electro catalytic activity to oxygen reduction reaction, result as shown in Figure 6, the mass activity (the dynamics current value at 0.95Vvs.RHE place) of Pt-Cu/MDC1-3 catalytic oxidation-reduction reaction is 374A/gPt, far above being purchased Pt/C-JM catalyst (46A/gPt).
Embodiment 4, to prepare tenor be 28.9wt%Pt-Cu alloy nanocluster complex catalyst Pt-Cu/MDC1-4 (method one)
By embodiment 2 gained Pt-Cu/MDC1-2 catalyst (50mg) ultrasonic disperse in the mixed solution of the nitric acid (18mL) of 0.75M, 0.1M sulfuric acid (1mL), 0.03M hydrochloric acid (1mL), be warming up to 300K, stir 4 hours, after being cooled to room temperature, centrifugation also washes precipitation with water to remove residual acid, gained solid product, in 333K vacuum drying 10 hours, obtains Pt-Cu alloy nanocluster complex catalyst Pt-Cu/MDC1-4.ICP-AES analyzes and shows, in Pt-Cu/MDC1-4, Pt/Cu atomic ratio is 70:30, Pt metal ladings is 25.4wt%.Tem analysis shows, in PtCu/MDC1-4, the average grain diameter of metal nanoparticle is 2.1 nanometers, and domain size distribution is 1.5-3.5 nanometer.
Embodiment 5, preparation bullion content are the PtRu alloy nanocluster complex catalyst PtRu/MDC1-5 (method one) of 30wt%
By 10mg melamine goes in 80mL ethanol, make melamine solution.(400mg, specific area is 680m to aza nanometer angle-graphite complex carbon material direct-current arc synthesized 2/ g, add in above-mentioned melamine solution by Chinese invention patent application (application number: 2012062500461210) described method preparation), ultrasonic process 20 minutes, boils off solvent in 353K heating, obtains melamine-aza nanometer angle-graphitic carbon mixture.Under the mixed atmosphere (nitrogen: oxygen partial pressure is than being 4:1) of nitrogen and oxygen, mixture is heated to 623K in tube furnace, be incubated and be cooled to room temperature after 1.5 hours, obtain the material with carbon element (MDC1-5) that melamine condensation polymer is modified, elementary analysis shows that in MDC1-5, nitrogen content is 1.8%, and its specific area is 540m 2/ g.
1.036g six hydration chloroplatinic acid and 0.415g ruthenium trichloride are dissolved in 50ml ethylene glycol, the ethylene glycol solution (1.0mol/L) getting 50mlNaOH joins wherein with vigorous stirring, at room temperature continue stirring 5 minutes, gained reactant to be refluxed 3 hours obtained Pt-Ru alloy nanocluster colloidal solution at 453K, be cooled to room temperature for subsequent use, wherein the concentration of metal (Pt, Ru) is 5.92g/L.
MDC1-5 (35mg) is added in 150ml acetone solvent, ultrasonic process 30 minutes (frequency 59kHz), Pt metal-Ru the colloidal solution of 4.05ml is added drop-wise in above-mentioned suspension under fast stirring, after above-mentioned mixed liquor is continued ultrasonic 30 minutes, continue stirring 36 hours, filter, gained sediment is placed in vacuum drying chamber, dry under 300K.By the black powder that obtains in tube furnace, under nitrogen atmosphere, be heated to 523K, be incubated 1 hour, spend deionized water after being cooled to room temperature and be precipitated to without Cl -ion detects, and will be deposited in 313K dried overnight in vacuum drying chamber, and obtained bullion content is the PtRu alloy nanocluster complex catalyst PtRu/MDC1-4 of 30wt%.ICP-AES test analysis shows, in PtRu/MDC1-5, the atomic ratio of Pt/Ru is 1:1.Tem analysis shows, in PtRu/MDC1-5, the average grain diameter of PtRu nano particle is 1.9 nanometers, and domain size distribution is 0.5-5.5 nanometer.
Catalysis electrode is prepared by method described in embodiment 1, in 333K, what nitrogen was saturated contains in the sulfuric acid solution (0.5M) of 1M methyl alcohol, mass activity (the 0.55Vvs.RHE of PtRu/MDC1-5 catalysis methanol oxidation reaction, 335mA/mgPtRu) be 2.6 times of commercial PtRu/C-JM (PtRu content 30wt%) catalyst (128mA/mgPtRu), show that PtRu/MDC1-5 catalyst has 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)
By 10mg melamine goes in 100mL acetone soln, make melamine solution.Conductive black (is purchased KetjenBlack, 0.4g, specific area 950m 2/ g) add in above-mentioned melamine solution, ultrasonic process 20 minutes, boils off solvent in 60 DEG C of heating, obtains melamine-KetjenBlack material with carbon element) mixture.Under an argon atmosphere, mixture is heated to 773K in Muffle furnace, is incubated and is cooled to room temperature after 20 minutes, obtain the material with carbon element MDC1-6 that melamine condensation polymer is modified, elementary analysis shows that in MDC1-6, nitrogen content is 0.5wt%, and its specific area is 850m 2/ g.
1g hydrate ruthenium trichloride is dissolved in 50ml ethylene glycol, the ethylene glycol solution (0.5mol/L) getting 50mlNaOH adds in the ethylene glycol solution of ruthenium trichloride with vigorous stirring, at room temperature continue stirring 5 minutes, under the condition that gained reactant is flowed through at nitrogen, to reflux 3 hours obtained ruthenium metal nanometre cluster colloidal solution in 453K, be cooled to room temperature for subsequent use, wherein the concentration of metal Ru is 3.86g/L.
MDC1-6 (90mg) is added in 150ml acetone, ultrasonic process 30 minutes, the metal Ru colloidal solution of 0.75ml is added drop-wise in above-mentioned suspension under fast stirring, after above-mentioned mixed liquor is continued ultrasonic 30 minutes, continue stirring 12 hours, filter, with acetone washing precipitation three times, gained solid sediment is heat treatment one hour in nitrogen atmosphere under 573K, grinds and spend deionized water to without Cl -ion is detected, by precipitation with after the washing of a small amount of ethanol in vacuum drying chamber under 333K dried overnight, obtained bullion content is the Ru metal nanometre cluster complex catalyst Ru/MDC1-6 of 3wt%.Tem analysis shows, in Ru/MDC1-6, the average grain diameter of Ru metal nanoparticle is 1.4 nanometers, and domain size distribution is 1-3 nanometer.
Embodiment 7, preparation bullion content are the Pt-Rh-Ir alloy nanocluster complex catalyst Pt-Rh-Ir/MDC1-7 of 3wt%) (method one)
Method in reference literature prepares carbon fiber (EveS.Steigerwalt, etal., J.Phys.Chem.B, 2002,106,760 – 766).
1g melamine goes in (ethanol/water volume ratio=1:1), is made melamine solution in 300mL ethanol water.Add in melamine solution by above-mentioned carbon fiber (2.5g), ultrasonic process 1 hour, in 160 DEG C of oil baths, heating boils off solvent, obtains melamine-carbon fiber mixture.In air atmosphere mixture is heated to 573K, is incubated and is cooled to room temperature after 1 hour, obtain the material with carbon element (MDC1-7) that melamine condensation polymer is modified, elementary analysis shows that in MDC1-7, nitrogen content is 15wt%.
0.5179g six hydration chloroplatinic acid, 0.0658g rhodium trichloride hydrate and 0.0882g hydrated iridium trichloride are dissolved in the mixed solution (ethylene glycol/glycerin volume ratio=5:1) of 50ml ethylene glycol and glycerine; under agitation the ethylene glycol solution (0.16mol/L) of 50mlNaOH is joined wherein; at room temperature continue stirring 5 minutes; gained reactant is refluxed in 473K under nitrogen protection and within 3 hours, obtains " non-protected type " Pt-Rh-Ir alloy nanocluster colloid; be cooled to room temperature for subsequent use, wherein the concentration of Pt metal-Rh-Ir is 2.69g/L.
Get 23ml gained Pt-Rh-Ir alloy nanocluster colloid, add 0.5mol/L sulfuric acid 95ml wherein, again Pt-Ru-Ir alloy nanocluster colloid is formed by being scattered in again after metal nanometre cluster precipitation and centrifugal separation in 25ml oxolane, then gained Pt-Ru-Ir alloy nanocluster colloid is joined under fast stirring 20ml and be dispersed with (ethanol/water volume ratio=1:1) in the ethanol water of the above-mentioned MDC1-7 of 2g, continue stirring 10 hours, adding formic acid makes system pH be 3, centrifugation precipitates, with water washing, in 353K vacuum drying 12 hours, namely obtained bullion content is the Pt-Rh-Ir alloy nanocluster complex catalyst Pt-Rh-Ir/MDC1-7 of 3wt%.Tem analysis shows, in Pt-Rh-Ir/MDC1-7, the average grain diameter of Pt-Rh-Ir alloy nanocluster is 2 nanometers, and domain size distribution is 1-4 nanometer, and EDX analyzes and shows that the atomic ratio of Pt-Rh-Ir alloy nano particle Pt:Rh:Ir is 4:1:1.
Select in the soluble-salt of Pt, Rh, Ru, Ir etc. or acid two or more, adopt method similar to Example 7, the alloy nanocluster complex catalyst containing these transition metal can be prepared.
Embodiment 8, prepare the Pt-Cu-Pd alloy nanocluster complex catalyst Pt-Cu-Pd/MDC1-8 (method one) of tenor 19.2wt%
By 100mg melamine goes in 80mL ethanol, make melamine solution.Nanometer angle-graphite complex carbon material (50mg) adds in melamine solution by aza described in embodiment 3, ultrasonic process 20 minutes, boils off solvent, obtain melamine-nanometer angle-graphite complex carbon material mixture in 353K heating.In a nitrogen atmosphere, mixture is heated to 673K, is incubated and is cooled to room temperature after 0.5 hour, obtain the material with carbon element MDC1-8 that melamine condensation polymer is modified, elementary analysis shows that in MDC1-8, nitrogen content is 18%.
By 31mg six hydration chloroplatinic acid, 26.5mg hydration Schweinfurt green Cu (CH 3cOO) 2h 2o and 1mg palladium is dissolved in 50ml ethylene glycol, with the ethylene glycol solution (0.25mol/L) of NaOH, the pH value of above-mentioned solution is adjusted to 10, under agitation being joined by gained mixed liquor is dispersed with in the 80ml ethylene glycol of 90mgMDC1-8, at room temperature continue stirring 5 minutes, by gained reactant in a nitrogen atmosphere, add hot reflux in 573K and be cooled to room temperature after 4 hours.Mixture is filtered, with water and ethanol washing solid sediment.By gained solid product vacuum drying 4h under 343K, i.e. obtained Pt-Cu-Pd alloy nanocluster complex catalyst Pt-Cu-Pd/MDC1-8.Tem analysis shows, in Pt-Cu-Pd/MDC1-8, the average grain diameter of alloy nano particle is 4.0 nanometers, and domain size distribution is 1-10 nanometer.ICP-AES analyzes and shows, the atomic ratio of Pt:Cu:Pd is 34:63:3.
Embodiment 9, prepare the Pt metal nanometre cluster complex catalyst Pt/MDC1-9 that tenor is 1wt%
By 60mg melamine goes in 80mL water, make melamine solution.Conductive carbon black (is purchased xC-72R, 100mg, specific area 254m 2/ g) add in above-mentioned melamine solution, ultrasonic process 30 minutes, in 150 DEG C of oil baths heating boil off aqueous solvent, obtain melamine-material with carbon element ( xC-72R) mixture.In air atmosphere, mixture is heated to 623K, is incubated and is cooled to room temperature after 40 minutes, obtain the material with carbon element MDC1-9 that melamine condensation polymer is modified, elementary analysis shows that in MDC1-9, nitrogen content is 11%, and its specific area is 80m 2/ g.
0.1g six hydration chloroplatinic acid is dissolved in 50ml ethylene glycol; get the aqueous solution (0.077mol/L) of 50ml NaOH; under agitation add in the ethylene glycol solution of chloroplatinic acid; stirring 25 minutes is continued in room temperature; gained reactant is added under nitrogen protection in 423K oil bath hot reflux 4 hours obtained " non-protected type " platinum nano-cluster colloids; be cooled to room temperature for subsequent use, wherein the concentration of Pt metal is 0.375g/L.Tem analysis shows, in platinum nano-cluster colloid, the average grain diameter of Pt metal nanometre cluster is 2.4 nanometers, and domain size distribution is 1.5-4.5 nanometer.
Get 5.4ml gained Pt nano-cluster colloid, add 1mol/L formic acid 5ml wherein, to again be scattered in 5ml oxolane after metal nanometre cluster precipitation and centrifugal separation, under fast stirring gained metal nanometre cluster colloid drops being added to 20ml is dispersed with in the acetone of MDC1-9 (0.2g), continue stirring 5 hours, precipitate in 353K air drying 12 hours after centrifugation, washing, namely obtained platinum content is the Pt metal nanometre cluster complex catalyst Pt/MDC1-9 of 1wt%.Tem analysis shows, in Pt/MDC1-9, the average grain diameter of Pt nano particle is 2.5 nanometers, and domain size distribution is 1.5-5 nanometer.
Embodiment 10, prepare the Pt metal nanometre cluster complex catalyst Pt/MDC1-10 that tenor is 1wt%
By 5mg melamine goes in 150mL water, make melamine solution.By conductive carbon black, (be purchased acetylene carbon black DenkablackAB, 0.5g, specific area is 60m 2/ g) add in above-mentioned melamine solution, ultrasonic process 20 minutes, in 150 DEG C of oil baths, heating boils off aqueous solvent, obtains melamine-material with carbon element (DenkablackAB) mixture.In air atmosphere, mixture is heated to 603K in Muffle furnace, is incubated and is cooled to room temperature after 1 hour, obtain the material with carbon element MDC1-10 that melamine condensation polymer is modified, elementary analysis shows that in MDC1-10, nitrogen content is 0.1%, and its specific area is 50m 2/ g.
By the method for embodiment 9, MDC1-9 is replaced to prepare the Pt metal nanometre cluster complex catalyst Pt/MDC1-10 that platinum content is 1wt% with MDC1-10.Tem analysis shows, in Pt/MDC1-10, the average grain diameter of Pt nano particle is 2.6 nanometers, and domain size distribution is 1.5-5.5 nanometer.
Embodiment 11, preparation Pt content are the Pt metal nanometre cluster complex catalyst (Pt/MDC1-11) of 50wt%
(method two)
1g six hydration chloroplatinic acid is dissolved in 50ml ethylene glycol; the ethylene glycol solution (0.5mol/L) getting 50mlNaOH under agitation adds in the ethylene glycol solution of chloroplatinic acid; at room temperature continue stirring 5 minutes; under the condition that gained reactant is flowed through at nitrogen; reflux in 453K and obtain " non-protected type " platinum nano-cluster colloidal solution in 3 hours; be cooled to room temperature for subsequent use, wherein the concentration of Pt metal is 3.7g/L.
In Muffle furnace, 1g melamine is heated to 623K in a nitrogen atmosphere, is incubated and is cooled to room temperature after 40 minutes and obtains melamine condensation polymer MD-2.Under agitation, MD-2 (10mg) is added the ethylene glycol solution of 80ml, drip the ethylene glycol solution (0.25mol/L) of NaOH wherein, regulate pH value of solution to 10, be heated to 443K, be incubated and be cooled to room temperature after 30 minutes, under agitation conductive black (is purchased Blackpearls2000,40mg, specific area 1500m 2/ g) add in above-mentioned mixed liquor, ultrasonic process 20 minutes.The Pt metal colloidal solution of 13.5ml is added drop-wise in above-mentioned suspension under fast stirring, ultrasonic process in 20 minutes is carried out to above-mentioned mixed liquor, stir 36 hours, filter, spend deionized water and be precipitated to without Cl -ion is detected, by the vacuum drying 5 hours under 353K of gained solid sediment, i.e. and obtained Pt metal nanometre cluster complex catalyst Pt/MDC1-11.ICP-AES test analysis shows, in Pt/MDC1-11 catalyst, Pt content is 50wt%.Tem analysis shows, in Pt/MDC1-10, the average grain diameter of Pt metal nanoparticle is 2.4 nanometers.Elementary analysis shows, in Pt/MDC1-11, nitrogen content is 5.5wt%.
Embodiment 12, preparation Pt content are the Pt metal nanometre cluster complex catalyst (Pt/MDC1-12) of 59wt%
(method two)
" non-protected type " Pt nano-cluster colloidal solution and melamine condensation polymer MD-2 is prepared by the method for embodiment 11.
Under agitation, MD-2 (20mg) is added the ethylene glycol solution of 120ml, with the ethylene glycol solution (0.25mol/L) of NaOH, the pH value of above-mentioned mixed solution is adjusted to 10, is heated to 443K, be incubated and be cooled to room temperature after 30 minutes.Under agitation conductive black (is purchased Blackpearls2000,20mg, specific area 1500m 2/ g) add in above-mentioned mixed liquor, ultrasonic process 1 hour.The Pt metal colloidal solution of 16.2ml is added drop-wise in above-mentioned suspension under fast stirring, ultrasonic process in 30 minutes is carried out to above-mentioned mixed liquor, stir 48 hours, add 10ml formic acid solution (1mol/L), continue vigorous stirring 24 hours, filter, spend deionized water and be precipitated to without Cl -ion is detected, by the vacuum drying 1 hour under 353K of gained solid sediment, i.e. and obtained Pt metal nanometre cluster complex catalyst Pt/MDC1-12.ICP-AES test analysis shows, in Pt/MDC1-12, Pt content is 59wt%.Tem analysis shows that the average grain diameter of Pt metal nanoparticle in Pt/MDC1-12 is 2.5 nanometers, and domain size distribution is 1-6.5 nanometer.Elementary analysis shows that in Pt/MDC1-12, nitrogen content is 12wt%.
Embodiment 13, to prepare tenor be 20wt%Pt-Ni alloy nanocluster complex catalyst (Pt-Ni/MDC1-13) (method two)
In Muffle furnace, 0.1g melamine is heated to 733K in air atmosphere, is incubated and is cooled to room temperature after 1 hour and obtains melamine condensation product MD-4.
By 65.6mg six hydration chloroplatinic acid and 1mgNi (CH 3cOO) 24H 2o is dissolved in 60ml ethylene glycol, with the ethylene glycol solution (0.25mol/L) of NaOH, the pH value of above-mentioned mixed solution is adjusted to 10, mixed liquor is under agitation joined in the ethylene glycol (80ml) containing CNT (50mg), Graphene (50mg) and MD-4 (24mg), said mixture is placed in microwave synthesizer water heating kettle, in a nitrogen atmosphere, be warming up to 333K, be incubated 10 minutes, change gas in reaction gas into nitrogen containing 1% hydrogen, again temperature is risen to 523K, after 523K reacts 3 minutes, be cooled to room temperature.Mixture is filtered, with water and ethanol washing solid sediment.By the vacuum drying 5 hours under 323K of gained solid sediment, namely obtained tenor is Pt-Ni alloy nanocluster complex catalyst Pt-Ni/MDC1-14.Tem analysis shows, in Pt-Ni/MDC1-14, the average grain diameter of Pt-Ni metal nanoparticle is 2 nanometers, and domain size distribution is 1-5 nanometer.EDX test analysis shows, in Pt-Ni/MDC1-14, Pt/Ni atomic ratio is 9:1, and elementary analysis shows that in Pt-Ni/MDC1-14, nitrogen content is 8wt%.
Embodiment 14, prepare the Pt metal nanometre cluster complex catalyst (Pt/MDC2-1) of tenor 10wt%
(method three)
" non-protected type " Pt nano-cluster colloidal solution is prepared by the method for embodiment 11.
Melamine (12.5mg) and cyanuric acid (12.5mg) are dissolved in 80mL water respectively.Conductive carbon black (is purchased xC-72R, 100mg, specific area 254m 2/ g) add in above-mentioned melamine solution, ultrasonic process 30 minutes, in 423K oil bath heating boil off aqueous solvent, obtain melamine-material with carbon element ( xC-72R) mixture.Gained solid mixture is added in cyanuric acid solution, ultrasonic process 1 hour, boil off solvent in 423K heating.Solid product is added in 500mL deionized water, ultrasonic 20min, be heated to 323K and keep this temperature to stir 1 hour, the washing excessive cyanuric acid of removing or melamine.After having washed, to filter and by filter cake at 323K, under vacuum condition dry 8 hours, obtain the material with carbon element MDC2-1 of the Derivatives Modified that melamine and cyanuric acid are formed.Elementary analysis shows that in MDC2-1, nitrogen content is 10wt%, and its specific area is 110m 2/ g.
MDC2-1 (90mg) is added the 200ml aqueous solution, ultrasonic process 10 minutes.The Pt metal colloidal solution of 2.7ml is added drop-wise in above-mentioned suspension under fast stirring, stirs 12 hours, filter, spend deionized water and be precipitated to without Cl -ion is detected.Gained solid product, in 323K vacuum drying 1 hour, obtains Pt metal nanometre cluster complex catalyst Pt/MDC2-1.
Accompanying drawing 7 is the XPS spectrum of the N1s of MDC2-1 and Pt/MDC2-1.The N1s electron binding energy of MDC2-1 is mainly distributed in 397-403eV scope.The N1s electron binding energy of Pt/MDC2-1 is mainly distributed in 396-402eV scope.
ICP-AES test analysis shows, in Pt/MDC2-1, Pt content is 10wt%.Tem analysis shows, in Pt/MDC2-1, the average grain diameter of Pt metal nanoparticle is 2.0 nanometers, and domain size distribution is 0.5-4.5 nanometer (Fig. 8).
Prepare catalysis electrode by method described in embodiment 1, in perchloric acid (0.1M) aqueous solution that 303K nitrogen is saturated, test the cyclic voltammogram (Fig. 9) of the Pt/C catalyst prepared by Pt/MDC2-1 and comparative example 2.Calculated the electrochemical surface area (ECSA) of Pt in catalyst at the electricity of Pt surface generation underpotential deposition suction/desorption by hydrogen.The ECSA of Pt/MDC2-1 and Pt/C catalyst is respectively 24 and 75m 2/ gPt.In two kinds of catalyst, Pt content is 10wt%, and Pt nano-particles size is more or less the same, and the ECSA of Pt/MDC2-1 is only 32% of Pt/C catalyst, illustrate in Pt/MDC2-1 building-up process, part Pt nanoparticle surface is covered by the derivative that melamine and cyanuric acid are formed, and the ECSA of Pt/MDC2-1 is significantly reduced.
By the electro catalytic activity of the Pt/MDC2-1 catalyst towards oxygen reduction reaction prepared by method testing example 14 described in embodiment 1, the mass activity (the dynamics current value at 0.9Vvs.RHE place) of Pt/MDC2-1 to oxygen reduction reaction is 364A/gPt, commercial Pt/C-JM catalyst (167A/gPt, Pt content 9.4wt%, ECSA are 87m 2/ gPt) 2 times, be 1.7 times of prepared Pt/C catalyst (214A/gPt).Although the ECSA of Pt/MDC2-1 is only about 30% of Pt/C-JM and Pt/C, but Pt/MDC2-1 to the mass activity of oxygen reduction reaction far above Pt/C-JM and Pt/C catalyst, show in Pt/MDC2-1 catalyst, there is synergic catalytic effect between Pt nano particle and described melamine derivative, form high catalytic activity system.
Embodiment 15, prepare the Pt metal nanometre cluster complex catalyst (Pt/MDC2-2) (method three) that tenor is 30wt%
" non-protected type " Pt nano-cluster colloidal solution is prepared by the method for embodiment 11.
Melamine (55mg) and cyanuric acid (55mg) are dissolved in respectively (volumn concentration of water is 50%) in 100mL alcohol water mixed solution.(BlackPearl2000,400mg, specific area is 1500m will to be purchased conductive carbon black 2/ g) add in melamine solution, ultrasonic process 20 minutes, solvent is boiled off in 403K heating, gained solid is added in cyanuric acid solution, ultrasonic process 1 hour, boils off solvent in 403K heating, washes gained solid with water, and under 353K dry 12 hours, obtain the material with carbon element MDC2-2 of the Derivatives Modified that melamine and cyanuric acid are formed.Elementary analysis shows that in MDC2-2, nitrogen content is 11wt%.
MDC2-2 (70mg) is added in 150ml water, ultrasonic process 10 minutes.The Pt metal colloidal solution of 8.1ml is added drop-wise in above-mentioned suspension under fast stirring, stirs 36 hours, filter, spend deionized water and be precipitated to without Cl -ion is detected.Gained solid product, in 313K vacuum drying 5 hours, obtains Pt metal nanometre cluster complex catalyst Pt/MDC2-2.ICP-AES test analysis shows, in Pt/MDC2-2, Pt content is 30wt%.The tem analysis of accompanying drawing 10 shows, in Pt/MDC2-2, the average grain diameter of Pt metal nanoparticle is 1.7 nanometers, and domain size distribution is 0.5-6 nanometer.
Compared for raw material cyanuric acid CA (a) in accompanying drawing 11, the XPS spectrum of N1s of MDC2-2 and Pt/MDC2-2 (c) prepared by melamine (b), embodiment 14.The N1s electron binding energy of cyanuric acid is mainly distributed in 399-403eV scope, and the N1s electron binding energy of melamine is mainly distributed in 397-401eV scope, and the electron binding energy at summit place is respectively 400.8 and 398.7eV.Be different from above-mentioned two situations, the N1s electron binding energy of the material with carbon element MDC2-2 of the Derivatives Modified that cyanuric acid and melamine are formed mainly is distributed in 396-403eV scope, and the electron binding energy at its summit place is 399.6eV.The N1s electron binding energy of Pt/MDC2-2 is mainly distributed in 397-402eV scope.Compared with MDC2-2, the electron binding energy (399.0eV) at the N1s summit place of Pt/MDC2-2 moves 0.6eV to low electron binding energy.
By the electro catalytic activity of the Pt/MDC2-2 catalyst towards oxygen reduction reaction prepared by characterizing method testing example 14 described in embodiment 1, the mass activity (the dynamics current value at 0.9Vvs.RHE place) of Pt/MDC2-2 to oxygen reduction reaction is 320A/gPt, is 1.9 times of commercial Pt/C-JM catalysis electrode (167A/gPt).
Embodiment 16, preparation Pt content are the Pt metal nanometre cluster complex catalyst (Pt/MDC2-3) (method three) of 90wt%
Melamine (60mg) and cyanuric acid (60mg) are dissolved in 100mL acetonitrile solution respectively.Conductive carbon black (Blackpearls2000 will be purchased, 400mg) add in cyanuric acid solution, ultrasonic process 20 minutes, under 333K, decompression steams solvent, gained solid is added in melamine solution, ultrasonic process 1 hour, heating volatilization under 373K, except desolventizing, solid product is added in 500mL deionized water, ultrasonic 30min, be heated to 333K and keep this temperature to stir 1 hour, washing, filters and by filter cake under 333K dry 12 hours, obtains the material with carbon element MDC2-3 of the Derivatives Modified that melamine and cyanuric acid are formed.Elementary analysis shows that in MDC2-3, nitrogen content is 11.5wt%.
" non-protected type " Pt nano-cluster colloidal solution is prepared by the method for embodiment 11.
MDC2-3 (10mg) is added the 200ml aqueous solution, ultrasonic process 10 minutes.The Pt metal colloidal solution of 24.3ml is added drop-wise in above-mentioned suspension under fast stirring, stirs 48 hours, regulate pH to 3 with aqueous formic acid, stir 5 hours, filter, spend deionized water and be precipitated to without Cl -ion is detected.Gained solid product, in 343K vacuum drying 8 hours, obtains Pt metal nanometre cluster complex catalyst Pt/MDC2-3.ICP-AES test analysis shows, in Pt/MDC2-3, Pt content is 90wt%.Tem analysis shows, in Pt/MDC2-3, the average grain diameter of Pt metal nanoparticle is 3.6 nanometers.
Comparative example 1, in Muffle furnace, 0.1g melamine is heated to 613K in air atmosphere, is incubated and is cooled to room temperature after 1 hour and obtains melamine condensation polymer (MD-1).Elementary analysis (C32.96; N63.87, H2.75), infrared spectrum (Figure 12) analysis shows, MD-1 is melem.The x-ray photoelectron spectroscopy (N1s) of MD-1 is shown in accompanying drawing 1.
Comparative example 2, prepare the Pt metal nanometre cluster complex catalyst (Pt/C) of tenor 10wt%
" non-protected type " Pt nano-cluster colloidal solution is prepared by the method for embodiment 11.
By the method supporting Pt nano-cluster of embodiment 14, MDC2-1 is changed into and is purchased xC-72R, other step is identical, preparation Pt metal nanometre cluster complex catalyst (Pt/C).ICP-AES test analysis shows, in Pt/C, Pt content is 10wt%.Tem analysis shows, in Pt/C, the average grain diameter of Pt metal nanoparticle is 2 nanometers, and domain size distribution is 0.5-4.5 nanometer.
The cyclic voltammogram of the Pt/C catalyst tested in perchloric acid (0.1M) aqueous solution that 303K nitrogen is saturated is shown in accompanying drawing 9.
By the electro catalytic activity of the test of characterizing method described in embodiment 1 Pt/C catalyst towards oxygen reduction reaction, the mass activity (the dynamics current value at 0.9Vvs.RHE place) of Pt/C to oxygen reduction reaction is 214A/gPt.

Claims (35)

1. a nano-complex, comprises melamine derivative, material with carbon element and nano-cluster; Wherein, the material forming described nano-cluster is transition metal or transition metal alloy;
The quality of described nano-cluster accounts for the 0.1-90% of described nano-complex gross mass;
The mass ratio of described material with carbon element and melamine derivative is 1:1-100:1.
2. nano-complex according to claim 1, is characterized in that: described nano-complex is made up of described melamine derivative, material with carbon element and nano-cluster;
Described transition metal is selected from least one of Pt, Ru, Pd, Rh and Ir; Transition metal in described transition metal alloy is selected from least two kinds in Pt, Ru, Pd, Au, Rh, Ir, Cu and Ni.
The particle diameter of the described nano-cluster recorded by electron microscope is 0.5 to 10 nanometer;
The quality of described nano-cluster accounts for the 1-60% of described nano-complex gross mass;
The mass ratio of described material with carbon element and melamine derivative is 5-30:1;
Described melamine derivative is selected from least one in the derivative that melamine condensation polymer and melamine and cyanuric acid formed.
3. nano-complex according to claim 2, is characterized in that: described melamine derivative adsorbs or is chemically bound in the surface of carbon material surface and/or described nano-cluster.
4. nano-complex according to claim 2, is characterized in that: described melamine derivative adsorbs or is chemically bound in carbon material surface, forms the material with carbon element that melamine derivative is modified; The specific area of the material with carbon element that described melamine derivative is modified is 40-1300m 2/ g; Nitrogen content is 0.1-30wt%, is preferably 1-30wt%.
5. nano-complex according to claim 2, is characterized in that: the specific area of described material with carbon element is 40-2000m 2/ g, is preferably 60-1500m 2/ g.
6. nano-complex according to claim 2, is characterized in that: described material with carbon element is selected from least one in conductive carbon black, active carbon, carbon nanohorn, N-doping carbon nanohorn, CNT, Graphene, mesoporous carbon, graphite and carbon fibre material.
7. nano-complex according to claim 2, is characterized in that: the N1s electron binding energy of the described nano-complex recorded by x-ray photoelectron spectroscopy is mainly distributed in 397 ~ 402eV scope.
8. nano-complex according to claim 2, is characterized in that: described melamine derivative is melamine condensation polymer;
The N1s electron binding energy of the x-ray photoelectron spectroscopy of described melamine condensation polymer is mainly distributed in 397 ~ 402eV scope.
9. nano-complex according to claim 8, is characterized in that: in described XPS spectrum, and N1s peak comprises graphite N ,-C=N-C ,-NH 2with the signal of amide groups.
10. nano-complex according to claim 8, is characterized in that: described melamine condensation polymer obtains according to the method preparation comprised the steps: by melamine polycondensation in a heated condition;
In described heating condition, temperature is specially 573-973K.
11. nano-complexes according to claim 8, is characterized in that: described melamine condensation polymer is at least one in melem and melem condensation polymer.
12. nano-complexes according to claim 2, is characterized in that: described nano-complex obtains according to the method preparation comprised the steps:
1) solution of melamine is mixed with the arbitrary described material with carbon element of at least one claim 3-6, heat-treat after removing solvent, be cooled to room temperature, obtain the material with carbon element MDC1 that melamine condensation polymer is modified;
2) acid of arbitrary at least one claim 1-4 described transition metal or soluble-salt are dissolved in alcohol or alcohol-water mixture, obtain the transistion metal compound solution that concentration is 0.01-100g/L, under agitation the alcoholic solution of the hydroxide of above-mentioned solution and alkali metal or alkaline-earth metal or the aqueous solution or alcohol solution are mixed, add step 1 again) gained melamine condensation polymer modify material with carbon element MDC1, through mixing, stir or ultrasonic process after, heat in 313-600K in reducing atmosphere or inert atmosphere, solid in separated and collected system, obtain described nano-complex.
13. nano-complexes according to claim 12, is characterized in that: described step 1) in, the concentration of the solution of melamine is 1 × 10 -3~ 10 2g/L, solvent is selected from water and can dissolves at least one in the organic compound of melamine;
The mass ratio of described material with carbon element and melamine is 1:2 ~ 100:1;
The method of described removal solvent is evaporation, filters or drying;
In described heat treatment step, atmosphere is inert atmosphere or oxygenous mixed-gas atmosphere; Heat treated temperature is 573-973K;
Described step 2) in, described alcohol is at least one in the derivative of the trihydroxylic alcohol of the monohydric alcohol of C1-C8, the dihydroxylic alcohols of C1-C8, the derivative of the dihydroxylic alcohols of C1-C8, the trihydroxylic alcohol of C1-C8 and C1-C8;
Wherein, the derivative of the dihydroxylic alcohols of described C1-C8 is specially the unitary methoxy or ethoxy derivative of the dihydroxylic alcohols of C1-C8;
The derivative of the trihydroxylic alcohol of described C1-C8 is specially the unitary methoxy or ethoxy derivative of the trihydroxylic alcohol of C1-C8;
In described alcohol-water mixture, the volumn concentration of water is 0-70%, is preferably 0-50%;
Described reducing atmosphere is the atmosphere containing hydrogen.
14. nano-complexes according to claim 2, is characterized in that: described nano-complex obtains according to the method preparation comprised the steps:
The acid of transition metal described at least one claim 1-4 or soluble-salt are dissolved in alcohol or alcohol-water mixture, obtain the transistion metal compound solution that concentration is 0.01-100g/L, under agitation by its with alkali metal or the alcoholic solution of the hydroxide of alkaline-earth metal or the aqueous solution or alcohol solution mix, according to proportioning, gained liquid is mixed with melamine condensation polymer described at least one claim 1-10 and material with carbon element again, stir or ultrasonic process after, heat in 313-600K in reducing atmosphere or inert atmosphere, solid in separated and collected system, obtain described nano-complex.
15. nano-complexes according to claim 14, is characterized in that: described alcohol is at least one in the derivative of the trihydroxylic alcohol of the monohydric alcohol of C1-C8, the dihydroxylic alcohols of C1-C8, the derivative of the dihydroxylic alcohols of C1-C8, the trihydroxylic alcohol of C1-C8 and C1-C8;
Wherein, the derivative of the dihydroxylic alcohols of described C1-C8 is specially the unitary methoxy or ethoxy derivative of the dihydroxylic alcohols of C1-C8;
The derivative of the trihydroxylic alcohol of described C1-C8 is specially the unitary methoxy or ethoxy derivative of the trihydroxylic alcohol of C1-C8;
In described alcohol-water mixture, the volumn concentration of water is 0-70%, is preferably 0-50%;
Described reducing atmosphere is the atmosphere containing hydrogen;
The mass ratio of described material with carbon element and melamine condensation polymer is 100:1-100; The mass ratio of described material with carbon element and metal is 10:0.01-90.
16. nano-complexes according to claim 2, is characterized in that: the derivative that described melamine and cyanuric acid are formed is the bond complexes that melamine and cyanuric acid are formed.
17. nano-complexes according to claim 16, is characterized in that: the N1s electron binding energy of the x-ray photoelectron spectroscopy of described nano-complex is mainly distributed in 397 ~ 403eV scope.
18. nano-complexes according to claim 16, is characterized in that: described nano-complex obtains according to the method preparation comprised the steps:
1) by material with carbon element Homogeneous phase mixing described in the one in melamine and cyanuric acid and at least one claim 3-6, then by the another kind in melamine and cyanuric acid and said mixture Homogeneous phase mixing; The product that above-mentioned mixing obtains is heat-treated, after being cooled to room temperature, obtains the material with carbon element MDC2 of melamine and cyanuric acid Derivatives Modified;
2) prepare metallic colloid: by the soluble-salt of transition metal described at least one claim 1-4 or containing the acid dissolve of described transition metal in alcohol or alcohol-water mixture, be mixed with the transistion metal compound solution that concentration is 0.01-100g/L, then the alcoholic solution of the hydroxide of alkali metal or alkaline-earth metal or the aqueous solution or alcohol solution is added, gained mixed liquor is heated at 343-533K, obtains described transition metal nano-cluster or alloy nanocluster colloidal solution;
3) by step 1) gained MDC2 is scattered in can in the mixed solvent of the organic solvent miscible with water or itself and water, obtained suspension; By step 2) gained transition metal nano-cluster colloidal solution and above-mentioned suspension be in transition metal: MDC2 mass ratio is the ratio mixing of 1:0.001-9, stir or ultrasonic process, isolate precipitation and by it under 273-673K, heat in inert atmosphere or reducing atmosphere or under reduced pressure, obtain described nano-complex.
19. nano-complexes according to claim 18, it is characterized in that: described step 1) in, the method of described mixing is by a kind of solution in melamine and cyanuric acid and described material with carbon element Homogeneous phase mixing, adopt the methods such as volatilization, evaporation, filtration by the solvent removing in this mixture, gained mixture is mixed with the alternative dissolution homogeneity in melamine and cyanuric acid, adopts volatilization, evaporation or filter the solvent removing in gained mixture; Described mixing, except the temperature of desolventizing or heat treatment step be 273-573K; The atmosphere of described heat treatment process is inert atmosphere or oxygenous mist;
The mass ratio of described melamine and cyanuric acid is 10:1 to 1:2; The concentration of described melamine and cyanuric acid solution is 0.1 ~ 10 2g/L; The solvent of described solution comprises water and can dissolve at least one in the organic compound of melamine and cyanuric acid; Described organic compound comprises compound or its mixtures such as alcohols, ketone, ester class and ethers;
Described step 2) in, described alcohol is at least one in the derivative of the trihydroxylic alcohol of the monohydric alcohol of C1-C8, the dihydroxylic alcohols of C1-C8, the derivative of the dihydroxylic alcohols of C1-C8, the trihydroxylic alcohol of C1-C8 and C1-C8; Wherein, the derivative of the dihydroxylic alcohols of described C1-C8 is specially the unitary methoxy or ethoxy derivative of the dihydroxylic alcohols of C1-C8; The derivative of the trihydroxylic alcohol of described C1-C8 is specially the unitary methoxy or ethoxy derivative of the trihydroxylic alcohol of C1-C8;
In described alcohol-water mixture, the volumn concentration of water is 0-50%;
Described precipitation of isolating comprises filtering or centrifugal mode is separated.
20. nano-complexes according to claim 12 or 18, is characterized in that: described method also comprises the steps:
With nano-complex described in claim 2 substitute described melamine derivative modify material with carbon element, and by step 2 described in claim 12) or claim 18 described in step 3) synthesize.
21. nano-complexes according to claim 12,14 or 18, is characterized in that: described method all also comprises the steps:
The nano-complex of the cupric of claim 12,14 or 18 gained and/or the alloy nanocluster of nickel is carried out chemical attack with the light transition metal of remove portion.
22. nano-complexes according to claim 21, is characterized in that: the method for described chemical attack is for using acid treatment, and described acid comprises at least one in nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid.
Nano-complex described in 23. claims 3,12,14 or 18, is characterized in that: the specific area of the material with carbon element that described melamine derivative is modified is 40-1300m 2/ g, preferred 50-1200m 2/ g.
24. nano-complexes according to claim 23, is characterized in that: the N1s peak of the x-ray photoelectron spectroscopy of the material with carbon element that described melamine derivative is modified covers 396 ~ 403.5eV scope.
25. 1 kinds of methods preparing nano-complex described in claim 2, comprise the steps:
1) solution of melamine is mixed with the arbitrary described material with carbon element of at least one claim 3-6, heat-treat after removing solvent, be cooled to room temperature, obtain the material with carbon element MDC1 that melamine condensation polymer is modified;
2) acid of arbitrary at least one claim 1-4 described transition metal or soluble-salt are dissolved in alcohol or alcohol-water mixture, obtain the transistion metal compound solution that concentration is 0.01-100g/L, under agitation the alcoholic solution of the hydroxide of above-mentioned solution and alkali metal or alkaline-earth metal or the aqueous solution or alcohol solution are mixed, add step 1 again) gained MDC1, after mixing, stirring or ultrasonic process, heat in 313-600K in reducing atmosphere or inert atmosphere, solid in separated and collected system, obtains described nano-complex.
26. methods according to claim 25, is characterized in that: described step 1) in, the concentration of the solution of melamine is 1 × 10 -3~ 10 2g/L, solvent is selected from water and can dissolves at least one in the organic compound of melamine;
The mass ratio of described material with carbon element and melamine is 1:2 ~ 100:1.
The method of described removal solvent is evaporation, centrifugation, filtration or drying;
In described heat treatment step, atmosphere is inert atmosphere or oxygenous mixed-gas atmosphere; Heat treated temperature is 573-973K;
Described step 2) in, described alcohol is at least one in the derivative of the trihydroxylic alcohol of the monohydric alcohol of C1-C8, the dihydroxylic alcohols of C1-C8, the derivative of the dihydroxylic alcohols of C1-C8, the trihydroxylic alcohol of C1-C8 and C1-C8;
Wherein, the derivative of the dihydroxylic alcohols of described C1-C8 is specially the unitary methoxy or ethoxy derivative of the dihydroxylic alcohols of C1-C8;
The derivative of the trihydroxylic alcohol of described C1-C8 is specially the unitary methoxy or ethoxy derivative of the trihydroxylic alcohol of C1-C8;
In described alcohol-water mixture, the volumn concentration of water is 0-70%, is preferably 0-50%;
Described reducing atmosphere is the atmosphere containing hydrogen.
27. methods according to claim 25, is characterized in that: described method also comprises the steps:
With nano-complex described in claim 2 substitute described melamine derivative modify material with carbon element, and by described step 2) step synthesize.
28. 1 kinds of methods preparing nano-complex described in claim 2, comprise the steps:
The acid of arbitrary at least one claim 1-4 described transition metal or soluble-salt are dissolved in alcohol or alcohol-water mixture, obtain the transistion metal compound solution that concentration is 0.01-100g/L, under agitation by its with alkali metal or the alcoholic solution of the hydroxide of alkaline-earth metal or the aqueous solution or alcohol solution mix, according to proportioning, gained liquid is mixed with the arbitrary described melamine condensation polymer of at least one claim 1-11 and material with carbon element again, stir or ultrasonic process after, heat in 313-600K in reducing atmosphere or inert atmosphere, solid in separated and collected system, obtain described nano-complex.
29. methods according to claim 28, is characterized in that: described alcohol is at least one in the derivative of the trihydroxylic alcohol of the monohydric alcohol of C1-C8, the dihydroxylic alcohols of C1-C8, the derivative of the dihydroxylic alcohols of C1-C8, the trihydroxylic alcohol of C1-C8 and C1-C8;
Wherein, the derivative of the dihydroxylic alcohols of described C1-C8 is specially the unitary methoxy or ethoxy derivative of the dihydroxylic alcohols of C1-C8;
The derivative of the trihydroxylic alcohol of described C1-C8 is specially the unitary methoxy or ethoxy derivative of the trihydroxylic alcohol of C1-C8;
In described alcohol-water mixture, the volumn concentration of water is 0-50%;
Described reducing atmosphere is the atmosphere containing hydrogen;
The mass ratio of described material with carbon element and melamine condensation polymer is 100:1-100; The mass ratio of described material with carbon element and metal is 10:0.01-90.
30. 1 kinds of methods preparing nano-complex described in claim 2, comprise the steps:
1) by the one in melamine and cyanuric acid and the arbitrary described material with carbon element Homogeneous phase mixing of at least one claim 3-6, then by the another kind in melamine and cyanuric acid and said mixture Homogeneous phase mixing; Above-mentioned suspension is heat-treated, after being cooled to room temperature, obtains the material with carbon element MDC2 of melamine and cyanuric acid Derivatives Modified;
2) prepare metallic colloid: by the soluble-salt of arbitrary at least one claim 1-4 described transition metal or containing the acid dissolve of described transition metal in alcohol or alcohol-water mixture, be mixed with the transistion metal compound solution that concentration is 0.01-100g/L, then the alcoholic solution of the hydroxide of alkali metal or alkaline-earth metal or the aqueous solution or alcohol solution is added, gained mixed liquor is heated at 343-533K, obtains described transition metal nano-cluster or alloy nanocluster colloidal solution;
3) by step 1) gained MDC2 adds can in the mixed solvent of the organic solvent miscible with water or itself and water, and ultrasonic process obtains suspension; By step 2) gained colloidal transition metal solution and above-mentioned suspension be in transition metal: MDC2 mass ratio is the ratio mixing of 1:0.001-9, stir or ultrasonic process, isolate precipitation and by it under 273-673K, process in inert atmosphere or reducing atmosphere or under reduced pressure, obtain described nano-complex.
31. methods according to claim 30, it is characterized in that: described step 1) in, the method of described mixing is by a kind of solution in melamine and cyanuric acid and described material with carbon element Homogeneous phase mixing, adopt the methods such as volatilization, centrifugation, evaporation, filtration by the solvent removing in this mixture, gained mixture is mixed with the alternative dissolution homogeneity in melamine and cyanuric acid, adopts the methods such as volatilization, evaporation, filtration by the solvent removing in this mixture; Described mixing, except the temperature of desolventizing or heat treatment step be 273-573K; The atmosphere of described heat treatment process is inert atmosphere or oxygenous mist;
The mass ratio of described melamine and cyanuric acid is 10:1 ~ 1:2; The concentration of described melamine and cyanuric acid solution is 0.1 ~ 10 2g/L; The solvent of described solution comprises water and can dissolve at least one in the organic compound of melamine and cyanuric acid; Described organic compound comprises compound or its mixtures such as alcohols, ketone, ester class and ethers; In addition, also can wash product in this step, cleaning solvent comprises water or conventional organic solvent, comprises alcohol, nitrile, ketone equal solvent; In described mixed solvent, the volumn concentration of water is 0-90%;
Described step 2) in, described alcohol is at least one in the derivative of the trihydroxylic alcohol of the monohydric alcohol of C1-C8, the dihydroxylic alcohols of C1-C8, the derivative of the dihydroxylic alcohols of C1-C8, the trihydroxylic alcohol of C1-C8 and C1-C8; Wherein, the derivative of the dihydroxylic alcohols of described C1-C8 is specially the unitary methoxy or ethoxy derivative of the dihydroxylic alcohols of C1-C8; The derivative of the trihydroxylic alcohol of described C1-C8 is specially the unitary methoxy or ethoxy derivative of the trihydroxylic alcohol of C1-C8;
In described alcohol-water mixture, the volumn concentration of water is 0-50%;
Described precipitation of isolating comprises filtering or centrifugal mode is separated.
32. methods according to claim 25 or 30, is characterized in that: described method also comprises the steps:
With nano-complex described in claim 2 substitute described melamine derivative modify material with carbon element, and by step 2 described in claim 25) or claim 30 described in step 3) synthesize.
33. methods according to claim 25,27,28,30 or 32, is characterized in that: described method all also comprises the steps:
The nano-complex of the cupric of method gained described in claim 25,27,28,30 or 32 and/or the alloy nanocluster of nickel is carried out chemical attack with the light transition metal of remove portion;
Described chemical attack is specially with acid treatment;
Described acid-specific comprises at least one in nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid.
The arbitrary described nano-complex of 34. claim 1-24 is as the application of electrochemical catalyst.
35. application according to claim 34, is characterized in that: the arbitrary described nano-complex of claim 1-24 is as the application of the catalyst of fuel cell reaction;
Described fuel cell reaction is specially oxygen reduction reaction or methanol oxidation.
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