CN103515627A - Nitrogen hybridized carbon nanohorn-graphite nanocomposite, and preparation method and application thereof - Google Patents
Nitrogen hybridized carbon nanohorn-graphite nanocomposite, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a nitrogen hybridized carbon nanohorn-graphite nanocomposite, a preparation method thereof and application of the nanocomposite as a catalyst carrier. A nanometer composite catalyst provided by the invention is composed of the nitrogen hybridized carbon nanohorn-graphite nanocomposite and a transition metal and/or transition metal alloy nano-cluster, wherein the mass percentage content of the transition metal and/or transition metal alloy nano-cluster is 0.1 to 80%, the size of the transition metal and/or transition metal alloy nano-cluster is 0.5 to 20 nm, and the transition metal and/or transition metal alloy nano-cluster is dispersed in a porous nanometer network formed by nitrogen hybridized carbon nanohorns and graphite. As a fuel cell catalyst, the nanometer composite catalyst has excellent electrocatalytic activity and stability in reactions like oxygen reduction and methanol oxidation.
Description
Technical field
The present invention relates to a kind of azepine carbon nanohorn-graphite composite nano materials and its preparation method and its application as catalyst carrier.
Background technology
Fuel cell is a kind of device that chemical energy is converted into electric energy, is 21 century one of the most attractive electricity-generating method.Energy density is high because having for the low-temperature fuel cells such as solid polymer membrane fuel cell (PEMFC) and direct alcohol fuel cell (DAFC), environmental friendliness, service conditions gentleness are easy to the advantages such as mobile, is expected to become the ideal power power supply of mobile and portable set.Load type platinum is noble metal catalyst based is the nucleus of this types of fuel cells, how when improving catalytic activity, strengthening the stability of catalyst, reduce the consumption of Pt metal to reduce costs, is the key issue that needs solution in low-temperature fuel cell practicalization.
The noble metal catalyst based performance of load type platinum is relevant to the physicochemical properties of metal and alloy nanocluster and carbon carrier, and interaction between metal and carrier can improve decentralization and the utilance of noble metal, contribute to improve electrocatalysis characteristic, strengthen the stability of eelctro-catalyst.Many azepine material with carbon elements have been used as electro-catalyst carrier, to improve catalytic activity and stability.
Under the employing ammonia atmospheres such as Thomas, heat treatment Vulcan XC-72 carbon black carries out azepine, utilizes hydrogen-peroxide reduction method (regulating pH=3 with sulfuric acid) to prepare the supporting platinum-based metal catalyst of azepine carbon black (Roy, S.C.; Christensen, P.A.; Hamnelt, A.; Thomas, K.M.; And Trapp, V.J.Electrochem.Soc., 1996,143,3073; Roy, S.C.; Harding, A.W.; RusseII, A.E.; And Thomas, K.M.; 1997,144,2323) the supporting platinum-based metal catalyst of not azepine carbon black of, preparing with same method is compared, its catalytic activity to oxygen reduction reaction and methanol oxidation is significantly increased, but its catalytic activity has been compared low with the existing Pt/C of being purchased catalyst nearly order of magnitude.It is carbon and nitrogenous source that Sun Xueliang etc. be take ethene and melamine, adopts chemical vapour deposition technique synthetic nitrogen hydridization carbon nano-tube (CNT), then utilize reduction of ethylene glycol legal system standby the supporting platinum-based metal catalyst of azepine carbon nano tube (Chen, Y.; Wang, J.; Liu, H.; Li, R.; Sun, X.; Ye, S.; Knights, S., Electrochemistry Communications2009,11,2071; Chen, Y.; Wang, J.; Liu, H.; Banis, M.N.; Li, R.; Sun, X.; Sham, T-K; Siyu Ye, and Knights, S., J.Phys.Chem.C2011,115,3769), the supporting platinum-based metal catalyst of not hydridization CNT of preparing with same method is compared, and it improves approximately 30% to the catalytic activity of oxygen reduction reaction and stability.
The supporting platinum-based metal catalyst of current known carbon also far can not meet the extensive practical requirement of low-temperature fuel cell from catalytic activity and stability.
Summary of the invention
The object of this invention is to provide a kind of azepine carbon nanohorn-graphite composite material and its preparation method and its application as catalyst carrier.
Azepine carbon nanohorn-graphite nanometer composite material provided by the invention is comprised of azepine carbon nanohorn and graphite;
Wherein, to account for the quality percentage composition of described nano composite material be 1-3% to nitrogen element;
The mass ratio of described azepine carbon nanohorn and graphite is 1: 0.02-0.6.
The mode of appearance of described graphite is bar/sheet;
Described graphite bar/sheet is interspersed in azepine carbon nanohorn assembly, forms high conductive porous network.
The preparation method of described azepine carbon nanohorn-graphite composite material comprises the steps: to add water and other reacting gas in the cavity of direct-current arc synthesizer, take graphite rod as negative electrode and anode, use direct current arc method to prepare after solid product, gained solid product is carried out to heat treated in air or the mist that is comprised of inert gas and oxygen, obtain azepine carbon nanohorn-graphite nanometer composite material;
Described other reacting gas is nitrogen or the mist that contains nitrogen; Wherein, the mist that contains nitrogen described in is the mist of at least one formation in dry air or nitrogen and following gas: carbon monoxide, oxygen and carbon dioxide;
Described water shared pressure ratio in reaction system is 0.1-90%, is specially 4-90%, 12-90%, 70-90%, 4-70%, 12-70% or 4-12%;
In the cavity of described direct-current arc synthesizer, reaction atmosphere pressure is at room temperature 1 * 10
4-9 * 10
4pa, is specially 2 * 10
4pa-9 * 10
4pa, 2 * 10
4pa-5 * 10
4pa or 5 * 10
4pa-9 * 10
4pa;
In described direct current arc method, discharging current is 80-120A;
In described heat treatment step, the time is 0.1-100 hour, is specially 0.1-10 hour or 0.1-4 hour or 0.1-1 hour or 4-10 hour, and temperature is 473-1073K;
The application of nano composite material provided by the invention in preparing fuel cell electrochemical catalyst and the catalyst of described azepine carbon nanohorn-graphite nanometer composite material and transition metal nano-cluster and transition metal alloy nanocluster formation, also belong to shielded scope.
Nano-composite catalyst provided by the invention, at least one in above-mentioned azepine carbon nanohorn-graphite composite material and following substances forms: transition metal nano-cluster and transition metal alloy nano-cluster;
Transition metal in described transition metal nano-cluster is selected from least one in Pt, Ru, Pd, Au, Rh, Ir, Cu and Os;
Transition metal in described transition metal alloy nano-cluster is selected from Pt, Ru, Pd, Au, Rh, Ir, Cu and Os at least two kinds;
The quality percentage composition that described transition metal nano-cluster or transition metal alloy nano-cluster account for described nano-composite catalyst is 0.1-80%, is specially 0.1-75%.The mass ratio of described transition metal nano-cluster and transition metal alloy nano-cluster is 1:0.01-100;
In above-mentioned nano-composite catalyst, the transition metal in described transition metal nano-cluster is selected from least one in Pt, Ru, Pd, Rh and Ir;
Transition metal in described transition metal alloy nano-cluster is selected from Pt, Ru, Pd, Rh and Ir at least two kinds.
The diameter of described transition metal nano-cluster or transition metal alloy nano-cluster is 0.5-20 nanometer.
Described metal or alloy nano-cluster is scattered in the porous nano network that above-mentioned azepine carbon nanohorn-graphite constructs.
The invention provides two kinds of methods of preparing described nano-composite catalyst, wherein, method one comprises the steps:
1) by the transistion metal compound solution obtaining in the soluble-salt of transition metal or the sour mixed liquor that is dissolved in alcohol or is formed by described alcohol and water, mix with the alcoholic solution of alkali metal or alkaline earth metal hydroxide or the aqueous solution or the mixed liquor that formed by described alcohol and water, obtain liquid A;
2) by described that azepine carbon nanohorn-graphite nanometer composite material is scattered in the organic solvent that can dissolve each other with water or obtains suspension-turbid liquid B the mixed liquor being comprised of described organic solvent and water, by described liquid A and described suspension-turbid liquid B mix separated after, gained is deposited in reducing atmosphere or inert atmosphere and is heated, obtain described nano-composite catalyst.
In described step 1), soluble-salt or the transition metal in acid of described transition metal are selected from least one in Pt, Ru, Pd, Au, Rh, Ir, Cu and Os, preferably at least one in Pt, Ru, Pd, Rh and Ir; Described alcohol is all selected from the monohydric alcohol that the total number of carbon atoms is 1-8, the dihydroxylic alcohols that the total number of carbon atoms is 1-8, the trihydroxy alcohol that the total number of carbon atoms is 1-8, the monobasic methoxy or ethoxy derivative of the dihydroxylic alcohols that the total number of carbon atoms is 1-8, the monobasic methoxyl group of the trihydroxy alcohol that the total number of carbon atoms is 1-8 and at least one in ethyoxyl derivative; In the mixed liquor being comprised of described alcohol and water, the volumn concentration of water is 0.1-50%;
The concentration of the solution of described transistion metal compound is 0.01-100g/L, preferably 0.1-30g/L;
Described step 2), in, described reducing atmosphere is the atmosphere that contains hydrogen; Described inert atmosphere can be selected from least one in nitrogen, argon gas and helium;
Described organic solvent that can be miscible with water is selected from least one in methyl alcohol, ethanol, acetone, acetonitrile, dimethyl formamide and oxolane;
In described heating steps, temperature is 353-673K, preferred 373-573K, and the time is 0.5-100 hour.
In addition, described preparation method also comprises: in described step 2) after heating steps, before separating step, also can to add in mixture acid solution make pH value be less than 7 and by mixture stir, standing processing.
Method two comprises the steps:
1) will in the soluble-salt of transition metal or the sour mixed liquor that is dissolved in alcohol or is formed by described alcohol and water, obtain transistion metal compound solution, mix rear heating with the alcoholic solution of alkali metal or alkaline earth metal hydroxide or the aqueous solution or the mixed liquor that formed by described alcohol and water, obtain colloidal transition metal solution A;
2) described azepine carbon nanohorn-graphite nanometer composite material be scattered in to the organic solvent that can dissolve each other with water or obtain suspension-turbid liquid B the mixed liquor being formed by described organic solvent and water, by described colloidal solution A and described suspension-turbid liquid B mix separated after, gained is deposited under inert atmosphere or reducing atmosphere or reduced pressure and is processed, obtain described nano-composite catalyst.
In the described step 1) of said method, soluble-salt or the transition metal in acid of described transition metal are selected from least one in Pt, Ru, Pd, Au, Rh, Ir, Cu and Os, preferably at least one in Pt, Ru, Pd, Rh and Ir; The concentration of described transistion metal compound solution is 0.01-100g/L, preferably 0.1-30g/L; In described heating steps, temperature is 373-473K, and the time is 0.5-100 hour;
The molar ratio of the alkali metal in described alkali metal or alkaline earth metal hydroxide or alkaline-earth metal and described transition metal is 3-30;
Described alcohol is all selected from the monohydric alcohol that the total number of carbon atoms is 1-8, the dihydroxylic alcohols that the total number of carbon atoms is 1-8, the trihydroxy alcohol that the total number of carbon atoms is 1-8, the monobasic methoxy or ethoxy derivative of the dihydroxylic alcohols that the total number of carbon atoms is 1-8, the monobasic methoxyl group of the trihydroxy alcohol that the total number of carbon atoms is 1-8 and at least one in ethyoxyl derivative; In the mixed liquor being comprised of described alcohol and water, the volumn concentration of water is 0.1-50%;
Described step 2), in, described reducing atmosphere is the atmosphere that contains hydrogen; Described inert atmosphere can be selected from least one in nitrogen, argon gas and helium; In described reduced pressure, vacuum degree is 10
3-10
5pa; In described treatment step, temperature is 298-1073K, preferred 353-773K, and the time is 0.5-100 hour;
Transition metal in described colloidal transition metal solution and the mass ratio of described azepine carbon nanohorn-graphite composite material are 1: 0.001-0.80;
Described organic solvent that can be miscible with water is selected from least one in methyl alcohol, ethanol, acetone, acetonitrile, dimethyl formamide and oxolane;
Described in described organic solvent and the mixed solvent that forms of water that can be miscible with water, the volumn concentration of water be 0.1-90%.
The application of the catalyst that the invention described above provides in preparing fuel cell, also belongs to protection scope of the present invention.
The preparation method of azepine carbon nanohorn-graphite nanometer composite material provided by the invention, the carbon supported precious metal catalyst of preparing with prior art is compared, the novel nano compound fuel-cell catalyst that the azepine carbon nanohorn-graphite nanometer composite material provided by the invention of take is prepared as structural motif, has higher catalytic activity and stability to fuel cell reactions such as hydrogen reduction, methanol oxidations.
In fuel-cell catalyst research field, the activity and the stability that improve noble metal catalyst significant simultaneously, is also that people attempt the difficult problem solving for a long time.Metal nanometre cluster provided by the invention-azepine carbon nanohorn-graphite composite catalyst is different from other load type metal catalyst, its architectural feature is that metal nanometre cluster and/or alloy nanocluster are scattered in the nanostructure porous, electrically conductive network of azepine carbon nanohorn and graphite (bar/sheet) formation, makes metal nanometre cluster be difficult for migration, grow up; Azepine carbon nanohorn wall has good in electronics, and be difficult for oxidized, the stronger electron interaction of existence between metal or alloy nano-cluster and above-mentioned carrier material; Special porous network structure in catalyst is conducive to electrolytical transmission.Said structure feature makes catalyst of the present invention have excellent catalyst activity and stability to fuel cell reactions such as hydrogen reduction or methanol oxidations.In addition azepine carbon nanohorn-graphite composite material preparation method of the present invention adopts the method that adds water and other reacting gas in the cavity of direct-current arc synthesizer, preparation shaping/flake graphite is interspersed in the special construction of azepine carbon nanohorn bunch, azepine carbon nanohorn and graphite ratio are 1:0.02-0.6, the degree of graphitization that has improved productive rate and the nano combined material with carbon element of described azepineization of azepine carbon nanohorn, this is conducive to improve stability and the catalytic activity of catalyst.These all cannot be known from the simple supposition of knowledge in the past.
For example, Pt metal nanometre cluster-azepine carbon nanohorn-graphite composite catalyst that embodiment 1 and embodiment 2 are prepared, to the catalytic activity of the oxygen reduction reaction dynamics current value of 0.9V vs.RHE place (using as evaluation index), be 1.75 times of commercial Pt/C-JM catalysis electrode, and in acid solution, oxygen reduction reaction had to excellent stability.
Pt-Ru metal nanometre cluster-azepine carbon nanohorn-graphite composite catalyst that embodiment 6 is prepared, the mass activity of its catalysis methanol oxidation reaction (0.5V vs.RHE) is commercial Pt-Ru/C-JM(30wt%Pt-Ru) 3.0 times of catalysis electrode.Show that Pt-Ru metal nanometre cluster-azepine carbon nanohorn-graphite composite catalyst has higher catalytic activity to methanol oxidation.
Reference examples, when not adding water and using dry air in the cavity of direct-current arc synthesizer, contains a large amount of spherical amorphous graphite in resulting azepine carbon nanohorn-graphite material, azepine carbon nanohorn and graphite ratio are 1:0.83.Take its Pt metal nanometre cluster-azepine carbon nanohorn-graphite composite catalyst (Pt/NCC preparing as carrier
dry-20) catalytic activity of oxygen reduction reaction (0.9V vs.RHE) is compared to Pt/NCC
add water-20(embodiment 2, in direct-current arc synthesizer cavity, adding the prepared azepine carbon nanohorn-graphite composite material of water is carrier) low 60-70%.
Accompanying drawing explanation
Fig. 1 is thermogravimetric analysis (TGA) collection of illustrative plates of azepine carbon nanohorn-graphite composite material of embodiment 1; TGA test condition: in air 0-600 ℃ (10 ℃/min of programming rate), 600 ℃ (keeping 3h), 600-900 ℃ (5 ℃/min of programming rate).
Fig. 2 is the electromicroscopic photograph of platinum nano-cluster-azepine carbon nanohorn-graphite composite catalyst of embodiment 1;
Fig. 3 is the x-ray diffractogram of powder of platinum nano-cluster-azepine carbon nanohorn-graphite composite catalyst of embodiment 1;
Fig. 4 is the catalytic activity of oxygen reduction reaction on platinum nano-cluster-azepine carbon nanohorn-graphite composite catalyst of embodiment 1;
Fig. 5 is the electrochemical stability of oxygen reduction reaction on platinum nano-cluster-azepine carbon nanohorn-graphite composite catalyst of embodiment 1;
Fig. 6 is platinum ruthenium metal nanometre cluster-azepine carbon nanohorn-graphite composite catalyst and the contrast of commercial PtRu/C catalyst to methanol oxidation catalytic performance of embodiment 6.
Fig. 7 is thermogravimetric analysis (TGA) collection of illustrative plates of the azepine carbon nanohorn-graphite composite material of reference examples; TGA test condition: in air 0-600 ℃ (10 ℃/min of programming rate), 600 ℃ (keeping 3h), 600-900 ℃ (5 ℃/min of programming rate).
Embodiment
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.
In direct-current arc synthesizer cavity, splash into 5ml water, other reacting gas is air, and making water shared pressure ratio in overall reaction gas is 70%, and in cavity, gas pressure is 5 * 10
4pa.Take graphite rod as negative electrode and anode, and the discharging current of direct-current arc is 110A, uses direct current arc method synthetic nitrogen hydridization carbon nanohorn-graphite composite material.By the 673K heat treated 4 hours in air of the solid product after electric discharge, obtain azepine carbon nanohorn-graphite nanometer composite material.Elementary analysis shows, in azepine carbon nanohorn-graphite nanometer composite material, nitrogen content is 1.6wt.%.
Fig. 1 is thermogravimetric analysis (TGA) collection of illustrative plates of azepine carbon nanohorn-graphite composite material, at 600 ° of thermal weight losses below C, is 88.4%, is mainly because the oxidation of nitrogen hybridized nanometer angle generates carbon dioxide; At 600 ° of thermal weight losses more than C, being 7.8%, is mainly that graphite oxidation generates carbon dioxide.Thermogravimetric analysis shows, in azepine carbon nanohorn-graphite nanometer composite material, the weight ratio of nitrogen hybridized nanometer angle and graphite is 1:0.09.
1g six hydration chloroplatinic acids are dissolved in 50ml ethylene glycol; the ethylene glycol solution (0.5mol/L) of getting 50ml NaOH adds in the ethylene glycol solution of chloroplatinic acid under vigorous stirring; at room temperature continue to stir 5 minutes; under the condition that gained reactant is passed through at nitrogen stream; in 453K, reflux and within 3 hours, make " non-protection type " platinum nano-cluster colloidal solution; be cooled to room temperature and obtain colloidal transition metal solution A, wherein the concentration of Pt metal is 3.7g/L.Granularmetric analysis shows, Pt metal nanometre cluster average grain diameter is 1.7 nanometers.
The above-mentioned nitrogen hybridized nanometer of 50mg angle-graphite composite material is added in the 50ml ethanol/water mixed solvent of 1: 1, ultrasonic dispersion 30 minutes (operating frequency 59KHz) obtains suspension-turbid liquid B, the Pt metal colloidal solution of 1.35ml (being also colloidal transition metal solution A) is added drop-wise in above-mentioned suspension-turbid liquid B under rapid stirring, above-mentioned mixed liquor is continued after ultrasonic 30 minutes, continue to stir 12 hours, filter, use deionized water washing precipitation extremely without Cl
-ion is detected, and precipitation, with heating under 573K 1 hour under nitrogen atmosphere in tube furnace after a small amount of ethanol washing, makes described platinum cluster-azepine carbon nanohorn-graphite composite (Pt/NCC-9).Inductively coupled plasma atomic emission (ICP-AES) test analysis shows, Pt content is 9wt.%.
Transmission electron microscope (TEM) photo of platinum cluster-azepine carbon nanohorn-graphite composite of embodiment mono-preparation as shown in Figure 2.In platinum cluster-azepine carbon nanohorn-graphite composite powder, the composite construction that azepine carbon nanohorn and graphite form is high-visible, the average grain diameter of nanometer angle cluster is 40-60 nanometer, the length 20-60 nanometer of graphite flake, graphite flake is interspersed in the concrete body of azepine carbon nanohorn, is woven into high-specific surface area electrical-conductive nanometer net, and Pt nano-cluster is scattered in the network of azepine carbon nanohorn-graphite composite material preferably, its average grain diameter is 1.9 nanometers, and particle diameter is distributed as 0.5-4 nanometer.
Fig. 3 is the X ray diffracting spectrum of platinum cluster-azepine carbon nanohorn-graphite composite.In collection of illustrative plates, 26.4 ° of signals of locating are diffraction maximums of graphite in sample, and 25.8 ° of diffraction maximums that the signal of locating is nitrogenize nanometer angle.39.8 °, the signal of 67.5 ° and 81.3 ° belongs to (111) of face-centred cubic structure Pt nano particle in catalyst, diffraction maximum corresponding to (220) and (311) crystal face.
The preparation of catalysis electrode: take prepared platinum cluster-azepine carbon nanohorn-graphite composite powder 10mg, ultrasonic dispersion in 5mL absolute ethyl alcohol adds 100 μ L in above-mentioned dispersion
solution, continues ultrasonic processing 20 minutes.The suspension-turbid liquid of drawing 20 μ L catalyst with liquid-transfering gun is added drop-wise to glass-carbon electrode surface, under room temperature air drying 0.5 hour, vacuumize 1 hour under 120 ° of C again, makes platinum cluster-azepine carbon nanohorn-graphite composite (Pt/NCC-9) catalysis electrode.
In the saturated perchloric acid solution of oxygen (0.1M), Pt/NCC-9 and be purchased Pt/C-JM(purchased from Johnson Matthey company) catalysis electrode lists in table one to the catalytic activity of oxygen reduction reaction.Dynamics current value calculates according to Koutecky-Levich formula, and 0.9V data are taken from Fig. 4 a.Improve quality active and specific activity of Pt/NCC catalysis electrode is 1.75 and 1.6 times of commercial Pt/C-JM catalysis electrode, shows that Pt/NCC catalysis electrode has higher catalytic activity to oxygen reduction reaction.
Table one, PtN/CC and be purchased the catalytic activity contrast of Pt/C-JM catalysis electrode to oxygen reduction reaction
Test condition: temperature: 303K, the perchloric acid solution that oxygen is saturated (0.1M), sweep speed: 10mV/s, sweep limits: 0.05-1.2Vvs RHE.
As shown in Figure 5, in the saturated perchloric acid solution of oxygen (0.1M), Pt/NCC-9 catalysis electrode is through 15000 electric potential scannings (0.6-1.1V vs.RHE that circulates, accelerated ageing experiment) after, its cathodic polarization curve almost overlaps with the cathodic polarization curve before its accelerated ageing experiment, Pt/NCC-9 catalysis electrode before and after above-mentioned accelerated ageing experiment catalysis electrode at 0.9V(vs.RHE) current density located is respectively 2.15 ± 0.06mA cm
-2(at first) and 2.09 ± 0.06mA cm
-2, showing that above-mentioned accelerated ageing experiment does not cause the catalytic activity of Pt/NCC-9 catalysis electrode to occur obviously decay, prepared platinum cluster-azepine carbon nanohorn-graphite composite catalysis electrode has excellent stability to oxygen reduction reaction in acid solution.
Air stream is passed in the cavity of direct-current arc synthesizer after 323K saturated steam, and making water shared pressure ratio in overall reaction gas is 12%, and in cavity, gas pressure is 9 * 10
4pa.Take graphite rod as negative electrode and anode, and the discharging current of direct-current arc is 120A, uses direct current arc method synthetic nitrogen hydridization carbon nanohorn-graphite composite material.By the 573K heat treated 10 hours in air of the solid product after electric discharge, make azepine carbon nanohorn-graphite nanometer composite material.Elementary analysis shows, in azepine carbon nanohorn-graphite nanometer composite material, nitrogen content is 1.8wt.%.The thermogravimetric analysis of azepine carbon nanohorn-graphite composite material shows, the weight ratio of nitrogen hybridized nanometer angle and graphite is 1: 0.4.
By embodiment 1 preparation Pt metal nanometre cluster colloidal solution (being also colloidal transition metal solution A).
The above-mentioned nitrogen hybridized nanometer of 40mg angle-graphite composite material is added in the mixed solvent of 50ml ethanol/water 2:1, ultrasonic dispersion 30 minutes (operating frequency 59KHz) obtains suspension-turbid liquid B, the Pt metal colloidal solution of 2.7ml (being also colloidal transition metal solution A) is added drop-wise in above-mentioned suspension-turbid liquid B under rapid stirring, above-mentioned mixed liquor is continued after ultrasonic 30 minutes, continue to stir 12 hours, filter, use deionized water washing precipitation extremely without Cl
-ion is detected, precipitation with a small amount of ethanol, wash after in tube furnace under nitrogen atmosphere under 673K heat treated 1 hour, make described platinum cluster-azepine carbon nanohorn-graphite composite.By ICP-AES test analysis, Pt content is 20wt.%.Tem analysis shows, the average grain diameter of Pt nano particle is 2.4 nanometers.
By method described in embodiment 1, prepare catalysis electrode, in the saturated perchloric acid solution of oxygen (0.1M), on Pt/NCC-20 electrode, the initial reduction potential of catalytic oxidation-reduction reaction is 1.09V(vs.RHE), its catalytic activity to oxygen reduction reaction is 1.6 times of commercial Pt/C-JM catalysis electrode.Show that Pt/NCC-20 catalysis electrode has higher catalytic activity to oxygen reduction reaction.
333K, in the saturated perchloric acid solution of oxygen (0.1M), Pt/C-JM catalysis electrode circulates after (0.6-1.1Vvs.RHE, accelerated ageing experiment) through 10000 electric potential scannings, and Pt/C-JM catalysis electrode is at 0.9V(vs.RHE) current density located is respectively 1.79 ± 0.06mA cm
-2(at first) and 1.20 ± 0.06mA cm
-2, catalytic activity has decayed 33%; Pt/NCC catalysis electrode is after same accelerated ageing experiment, at 0.9V(vs.RHE) current density located is respectively 2.44 ± 0.08mA cm
-2(at first) and 2.22 ± 0.08mA cm
-2, showing that above-mentioned accelerated ageing experiment does not cause the catalytic activity of Pt/NCC catalysis electrode to occur obviously decay, prepared platinum cluster-azepine carbon nanohorn-graphite composite catalysis electrode has excellent stability to oxygen reduction reaction in acid solution.
Nitrogen is flowed through after 303K saturated steam and passed in the cavity of direct-current arc synthesizer, and making water shared pressure ratio in overall reaction gas is 4%, and in cavity, gas pressure is 2 * 10
4pa.Take graphite rod as negative electrode and anode, and the discharging current of direct-current arc is 80A, uses direct current arc method synthetic nitrogen hydridization carbon nanohorn-graphite composite material.By the 873K heat treated 1 hour in nitrogen of the solid product after electric discharge, make azepine carbon nanohorn-graphite nanometer composite material.Elementary analysis shows, in azepine carbon nanohorn-graphite nanometer composite material, nitrogen content is 2.5wt.%.The thermogravimetric analysis of azepine carbon nanohorn-graphite composite material shows, the weight ratio of nitrogen hybridized nanometer angle and graphite is 1: 0.5.
1g six hydration chloroplatinic acids are dissolved in 25ml ethylene glycol; the ethylene glycol solution (0.25mol/L) of getting 50ml NaOH adds in the ethylene glycol solution of chloroplatinic acid under vigorous stirring; at room temperature continue to stir 30 minutes; under the condition that gained reactant is passed through at nitrogen stream; in 433K, reflux and within 3 hours, make " non-protection type " platinum nano-cluster colloidal solution (being also colloidal transition metal solution A); be cooled to room temperature standby, wherein the concentration of Pt metal is 7.4g/L.Granularmetric analysis shows, Pt metal nanometre cluster average grain diameter is 2.0 nanometers.
13.3mg nitrogen hybridized nanometer angle-graphite composite material is added in the 50ml ethanol/water mixed solvent of 5: 1, ultrasonic dispersion 30 minutes (operating frequency 59KHz) obtains suspension-turbid liquid B, the Pt metal colloidal solution of 5.4ml (being also colloidal transition metal solution A) is added drop-wise in above-mentioned suspension-turbid liquid B under rapid stirring, above-mentioned mixed liquor is continued after ultrasonic 30 minutes, continue to stir 12 hours, filter, use deionized water washing precipitation extremely without Cl
-ion is detected, and precipitation, with heating under 373K 2 hours under nitrogen atmosphere in tube furnace after a small amount of ethanol washing, makes platinum cluster/azepine carbon nanohorn-graphite composite.By ICP-AES test analysis, Pt content is 75wt.%.Tem analysis shows, the average grain diameter of Pt nano particle is 2.5 nanometers.
In direct-current arc synthesizer cavity, splash into 6.5ml water, other reacting gas is air, and making water shared pressure ratio in overall reaction gas is 90%, and in cavity, gas pressure is 5 * 10
4pa.Take graphite rod as negative electrode and anode, and the discharging current of direct-current arc is 80A, uses direct current arc method synthetic nitrogen hydridization carbon nanohorn-graphite composite material.By the 1073K heat treated 0.1 hour in argon gas of the solid product after electric discharge, make azepine carbon nanohorn-graphite nanometer composite material.Elementary analysis shows, in azepine carbon nanohorn-graphite nanometer composite material, nitrogen content is 2.1wt.%.The thermogravimetric analysis of azepine carbon nanohorn-graphite composite material shows, the weight ratio of nitrogen hybridized nanometer angle and graphite is 1: 0.03.
0.14g tri-hydration osmium trichlorides are dissolved in 100ml ethylene glycol; the ethylene glycol solution (0.25mol/L) of getting 25ml NaOH adds in the ethylene glycol solution of osmium trichloride under vigorous stirring; at room temperature continue to stir 30 minutes; under the condition that gained reactant is passed through at nitrogen stream; in 433K, reflux and within 3 hours, make " non-protection type " osmium metal nanometre cluster colloidal solution (being also colloidal transition metal solution A); be cooled to room temperature standby, wherein the concentration of metal Os is 0.37g/L.Granularmetric analysis shows, Os metal nanometre cluster average grain diameter is 0.8 nanometer.
50mg nitrogen hybridized nanometer angle-graphite composite material is added in the 50ml ethanol/water mixed solvent of 3: 1, ultrasonic dispersion 30 minutes (operating frequency 59KHz) obtains suspension-turbid liquid B, the metal Os colloidal solution of 0.14ml (being also colloidal transition metal solution A) is added drop-wise in above-mentioned suspension-turbid liquid B under rapid stirring, above-mentioned mixed liquor is continued after ultrasonic 30 minutes, continue to stir 12 hours, filter, use deionized water washing precipitation extremely without Cl
-ion is detected, and precipitation, with heating under 673K 0.5 hour under nitrogen atmosphere in tube furnace after a small amount of ethanol washing, makes platinum cluster/azepine carbon nanohorn-graphite composite.By ICP-AES test analysis, Os content is 0.1wt.%.Tem analysis shows, the average grain diameter of Os nano particle is 0.9 nanometer.
By method described in embodiment 1, prepare azepine carbon nanohorn-graphite nanometer composite material.
21.6mg hydration Schweinfurt green is added in 8ml ethylene glycol, 333K heating is dissolved hydration Schweinfurt green, then in system, add 1.4mL six hydration chloroplatinic acid ethylene glycol solutions (0.02g/mL), the ethylene glycol solution (0.5mol/L) of getting 10ml NaOH adds in mixed solution under vigorous stirring, at room temperature continue to stir 5 minutes, gained reactant is refluxed and within 5 hours, makes Pt-Cu alloy nanocluster colloidal solution (being also colloidal transition metal solution A) at 470K, be cooled to room temperature standby.
The above-mentioned azepine carbon nanohorn-graphite composite of 88.1mg is put into the ultrasonic dispersion of 34.3mL ethylene glycol 30 minutes (being also suspension-turbid liquid B), above-mentioned Pt metal-Cu colloidal solution (being also colloidal transition metal solution A) is added drop-wise in suspension-turbid liquid B under rapid stirring, above-mentioned mixed liquor is continued after ultrasonic 2 hours, after being down to room temperature, filter, by deionized water and absolute ethanol washing precipitation, after washing of precipitate in vacuum drying chamber under 313K dried overnight, make platinoid metal nanometre cluster-azepine carbon nanohorn-graphite composite.By ICP-AES test analysis, Pt content is 8.1wt.%, and Cu content is 5.5wt.%, and the atomic ratio of Pt:Cu is 1:2.Tem analysis shows, the average grain diameter of Pt1Cu2 nano-cluster is 3.8 nanometers.
By method described in embodiment 1, prepare catalysis electrode, in the saturated perchloric acid solution of oxygen (0.1M), on Pt1Cu2/NCC electrode, the initial reduction potential of catalytic oxidation-reduction reaction is 1.09V(vs.RHE), the dynamics current value of its catalytic oxidation-reduction reaction is 3.3 times of commercial Pt/C-JM catalysis electrode.Show that Pt1Cu2/NCC catalysis electrode has higher catalytic activity to oxygen reduction reaction.
In above-mentioned synthesizing, change Pt/Cu ratio, can obtain Pt/Cu is 1: 10-10: 1 Pt-Cu/NCC catalyst.XRD characterization result shows, in prepared catalyst, metal is Pt-Cu alloy.
Embodiment 6, preparation Pt-Ru metal nanometre cluster-azepine carbon nanohorn-graphite composite (method two)
1.036g six hydration chloroplatinic acids and 0.415g ruthenium trichloride are dissolved in 50ml ethylene glycol; the ethylene glycol solution (1.0mol/L) of getting 50ml NaOH joins wherein under vigorous stirring; at room temperature continue to stir 5 minutes; gained reactant is refluxed and within 3 hours, makes " non-protection type " Pt-Ru alloy nanocluster colloidal solution (being also colloidal transition metal solution A) at 453K; be cooled to room temperature standby, wherein the concentration of Pt metal-Ru is 5.92g/L.
By method described in embodiment 2, prepare azepine carbon nanohorn-graphite nanometer composite material.
The above-mentioned azepine carbon nanohorn-graphite composite material of 35mg is added in 150ml acetone solvent, ultrasonic dispersion 30 minutes (operating frequency 59KHz) obtains suspension-turbid liquid B, Pt metal-Ru colloidal solution of 4.05ml (being also transition metal alloy colloidal solution A) is added drop-wise in above-mentioned suspension-turbid liquid B under rapid stirring, above-mentioned mixed liquor is continued after ultrasonic 30 minutes, continue to stir 36 hours, filter, the powder obtaining is placed under vacuum drying chamber room temperature dry.The black powder obtaining is in tube furnace under nitrogen atmosphere, 5K/min is heated to 573K, keep 1 hour, after being cooled to room temperature, with deionized water washing precipitation, extremely without Cl-ion, detect, to be deposited in vacuum drying chamber dried overnight under 313K, make platinum ruthenium nano-cluster-azepine carbon nanohorn-graphite composite.By ICP-AES test analysis, Pt content is 19.2wt.%, and Ru content is 9.7wt.%, and the atomic ratio of Pt:Ru is 1:1.Tem analysis shows, the average grain diameter of PtRu nano-cluster is 2.3 nanometers.
By method described in embodiment 1, prepare catalysis electrode, 333K, in saturated the containing in the sulfuric acid solution (0.5M) of 1M methyl alcohol of nitrogen, on Pt-Ru/NCC electrode, the initial oxidation current potential of methanol oxidation is 0.23V(vs.RHE), the mass activity of its catalysis methanol oxidation reaction (0.5V vs.RHE) is commercial Pt-Ru/C-JM(30wt%Pt-Ru) 3 times of catalysis electrode, as shown in Figure 6.Show that Pt-Ru/NCC catalysis electrode has higher catalytic activity to methanol oxidation.
Embodiment 7, preparation Ru metal nanometre cluster-azepine carbon nanohorn-graphite composite (Ru/NCC-3) (method two)
1g hydrate ruthenium trichloride is dissolved in 50ml ethylene glycol; the ethylene glycol solution (0.5mol/L) of getting 50ml NaOH adds in the ethylene glycol solution of ruthenium trichloride under vigorous stirring; at room temperature continue to stir 5 minutes; under the condition that gained reactant is passed through at nitrogen stream; in 453K, reflux and within 3 hours, make " non-protection type " ruthenium metal nanometre cluster colloidal solution (being also colloidal transition metal solution A); be cooled to room temperature standby, wherein the concentration of metal Ru is 3.86g/L.Granularmetric analysis shows, Ru metal nanometre cluster average grain diameter is 1.3 nanometers.
By method described in embodiment 1, prepare azepine carbon nanohorn-graphite nanometer composite material.
The above-mentioned azepine carbon nanohorn-graphite composite of 90mg is entered in 150ml acetone, ultrasonic dispersion 30 minutes (operating frequency 59KHz) obtains suspension-turbid liquid B, the metal Ru colloidal solution of 0.75ml (being also colloidal transition metal solution A) is added drop-wise in above-mentioned suspension-turbid liquid B under rapid stirring, above-mentioned mixed liquor is continued after ultrasonic 30 minutes, continue to stir 12 hours, filter, with acetone washing precipitation three times, gained pressed powder is heat treatment one hour in nitrogen atmosphere under 573K, grinds also with deionized water washing to without Cl
-ion is detected, precipitation with a small amount of ethanol, wash after in vacuum drying chamber under 333K dried overnight, (Ru content is: 3wt.%) to make described ruthenium metal nanometre cluster-azepine carbon nanohorn-graphite composite.
Embodiment 8, prepare metal nanometre cluster-metal alloy nano-cluster-azepine carbon nanohorn-graphite composite (Pd& Pt-Ru/NCC) (method two)
By method described in embodiment 1, prepare azepine carbon nanohorn-graphite nanometer composite material.
1g six hydration chloroplatinic acids are dissolved in 50ml ethylene glycol; the ethylene glycol solution (0.5mol/L) of getting 50ml NaOH adds in the ethylene glycol solution of chloroplatinic acid under vigorous stirring; at room temperature continue to stir 5 minutes; under the condition that gained reactant is passed through at nitrogen stream; in 453K, reflux and within 3 hours, to make " non-protection type " platinum nano-cluster colloidal solution to be cooled to room temperature standby, wherein the concentration of Pt metal is 3.7g/L.
1.036g six hydration chloroplatinic acids and 0.415g ruthenium trichloride are dissolved in 50ml ethylene glycol; the ethylene glycol solution (1.0mol/L) of getting 50ml NaOH joins wherein under vigorous stirring; at room temperature continue to stir 5 minutes; gained reactant is refluxed and within 3 hours, makes " non-protection type " Pt-Ru alloy nanocluster colloidal solution at 453K; be cooled to room temperature standby; wherein the concentration of Pt metal-Ru is 5.92g/L, and the atomic ratio of Pt:Ru is 1:1.
The above-mentioned azepine carbon nanohorn-graphite composite material of 35mg is added in 150ml acetone solvent, ultrasonic dispersion 30 minutes (operating frequency 59KHz) obtains suspension-turbid liquid B, the Pt metal colloidal solution of Pt metal-Ru colloidal solution of 4.0ml and 1.35ml is added drop-wise in above-mentioned suspension-turbid liquid B under rapid stirring, Pt metal nanometre cluster: the mass ratio of PtRu alloy nanocluster is 1:4.7, above-mentioned mixed liquor is continued after ultrasonic 30 minutes, continue to stir 36 hours, filter, the powder obtaining is placed under vacuum drying chamber room temperature dry.The black powder obtaining is in tube furnace under nitrogen atmosphere, and 5K/min is heated to 573K, keeps 1 hour, is cooled to after room temperature with deionized water washing precipitation to without Cl
-ion detects, and will be deposited in vacuum drying chamber dried overnight under 313K, makes platinum cluster-platinum ruthenium nano-cluster-azepine carbon nanohorn-graphite composite.By ICP-AES test analysis, Pt content is 19.5wt.%, and Ru content is 7.8wt.%.Tem analysis shows, the average grain diameter of metal nanoparticle is 2.2 nanometers.
In above-mentioned synthesizing, change Pt metal-Ru colloidal solution and Pt metal colloidal solution ratio, the mass ratio that can obtain Pt metal nanometre cluster/PtRu alloying metal nano-cluster is 1: 100-100: platinum cluster-platinum ruthenium nano-cluster-azepine carbon nanohorn-graphite composite catalyst of 1.
Embodiment 9, preparation Pt metal nanometre cluster-azepine carbon nanohorn-graphite composite (Pt wt.%:30%, Pt/NCC-30) (method one)
0.1g six hydration chloroplatinic acids are dissolved in 10ml ethylene glycol, and the ethylene glycol solution (0.5mol/L) of getting 10ml NaOH adds in the ethylene glycol solution of chloroplatinic acid under vigorous stirring, at room temperature continues to stir 30 minutes, obtains solution A.
By method described in embodiment 1, prepare azepine carbon nanohorn-graphite nanometer composite material.
The above-mentioned nitrogen hybridized nanometer of 50mg angle-graphite composite material is added in the 50ml ethanol/water mixed solvent of 1: 1, ultrasonic dispersion 30 minutes (operating frequency 59KHz) obtains suspension-turbid liquid B, the solution A of 7.92ml is added drop-wise under rapid stirring in above-mentioned suspension-turbid liquid B, above-mentioned mixed liquor is continued after ultrasonic 30 minutes, continue to stir 12 hours, filter, to be deposited in tube furnace under hydrogen atmosphere reductase 12 hour under 573K, make described platinum cluster-azepine carbon nanohorn-graphite composite (Pt/NCC-30).Inductively coupled plasma atomic emission (ICP-AES) test analysis shows, Pt content is 30wt.%.Tem analysis shows, the average grain diameter of metal nanoparticle is 2.4 nanometers.
Reference examples, preparation Pt metal nanometre cluster-azepine carbon nanohorn-graphite composite (Pt wt.%:19.7%, Pt/NCC-20
dry)
By introducing the cavity of direct-current arc synthesizer after air stream drying tower, anhydrous in cavity, other condition is prepared azepine carbon nanohorn-graphite composite material and Pt metal nanometre cluster-azepine carbon nanohorn-graphite composite catalyst by method described in embodiment 2.
Fig. 7 thermogravimetric analysis shows, while not adding water in the cavity of direct-current arc synthesizer, in prepared azepine carbon nanohorn-graphite composite material, the weight ratio of nitrogen hybridized nanometer angle and graphite is not 1: 0.8.Tem analysis shows, contains a large amount of spherical amorphous graphite in resulting azepine carbon nanohorn-graphite material.
By method described in embodiment 1, prepare catalysis electrode, in the saturated perchloric acid solution of oxygen (0.1M), Pt/NCC
dryon-20 electrodes, the initial reduction potential of catalytic oxidation-reduction reaction is 1.01V(vs.RHE), Pt/C-JM catalyst is suitable with being purchased, and it compares low (embodiment 2) 60-70% to the catalytic activity of oxygen reduction reaction (0.9V vs.RHE) with Pt/NCC-20.
Claims (10)
1. a nano composite material, is comprised of azepine carbon nanohorn and graphite;
Wherein, to account for the quality percentage composition of described nano composite material be 1-3% to nitrogen element;
The mass ratio of described azepine carbon nanohorn and graphite is 1:0.02-0.6.
2. material according to claim 1, is characterized in that: the mode of appearance of described graphite is bar/sheet;
Described graphite is interspersed in azepine carbon nanohorn assembly and forms network.
3. a method of preparing nano composite material described in claim 1 or 2, comprise the steps: to add water and other reacting gas in the cavity of direct-current arc synthesizer, take graphite rod as negative electrode and anode, use direct current arc method to prepare after solid product, gained solid product is carried out to heat treated in air or the mist that is comprised of inert gas and oxygen, obtain azepine carbon nanohorn-graphite nanometer composite material;
Described other reacting gas is nitrogen or the mist that contains nitrogen; Wherein, the mist that contains nitrogen described in is the mist of at least one formation in dry air or nitrogen and following gas: carbon monoxide, oxygen and carbon dioxide;
Described water shared pressure ratio in reaction system is 0.1-90%;
In the cavity of described direct-current arc synthesizer, reaction atmosphere pressure is at room temperature 1 * 10
4-9 * 10
4pa;
In described direct current arc method, discharging current is 80-120A;
In described heat treatment step, the time is 0.1-100 hour, and temperature is 473-1073K.
4. the catalyst that contains nano composite material described in claim 1 or 2.
5. a nano-composite catalyst, at least one in nano composite material described in claim 1 or 2 and following substances forms: transition metal nano-cluster and transition metal alloy nano-cluster;
Transition metal in described transition metal nano-cluster is selected from least one in Pt, Ru, Pd, Au, Rh, Ir, Cu and Os;
Transition metal in described transition metal alloy nano-cluster is selected from Pt, Ru, Pd, Au, Rh, Ir, Cu and Os at least two kinds;
The quality percentage composition that described transition metal nano-cluster or transition metal alloy nano-cluster account for described nano-composite catalyst is 0.1-80%;
The mass ratio of described transition metal nano-cluster and transition metal alloy nano-cluster is 1:0.01-100;
6. nano-composite catalyst according to claim 5, is characterized in that: the transition metal in described transition metal nano-cluster is selected from least one in Pt, Ru, Pd, Rh and Ir;
Transition metal in described transition metal alloy nano-cluster is selected from Pt, Ru, Pd, Rh and Ir at least two kinds.
7. according to the arbitrary described nano-composite catalyst of claim 5-6, it is characterized in that: the diameter of described transition metal nano-cluster or transition metal alloy nano-cluster is 0.5-20 nanometer;
Described metal or alloy nano-cluster is scattered in the network of being constructed by described azepine carbon nanohorn and graphite.
8. a method of preparing the arbitrary described nano-composite catalyst of claim 5-7, is following method one or method two,
Wherein, described method one comprises the steps:
1) will in the soluble-salt of transition metal or the sour mixed liquor that is dissolved in alcohol or is formed by described alcohol and water, obtain transistion metal compound solution, mix with the alcoholic solution of the hydroxide of alkali metal or alkaline-earth metal or the aqueous solution or the mixed liquor that formed by described alcohol and water, obtain liquid A;
2) nano composite material described in claim 1 or 2 be scattered in to the organic solvent that can dissolve each other with water or obtain suspension-turbid liquid B the mixed liquor being formed by described organic solvent and water, by described liquid A and described suspension-turbid liquid B mix separated after, gained is deposited in reducing atmosphere or inert atmosphere and is heated, obtain described nano-composite catalyst;
Described method two comprises the steps:
1) will in the soluble-salt of transition metal or the sour mixed liquor that is dissolved in alcohol or is formed by described alcohol and water, obtain transistion metal compound solution, mix rear heating with the alcoholic solution of alkali metal or alkaline earth metal hydroxide or the aqueous solution or the mixed liquor that formed by described alcohol and water, obtain colloidal transition metal solution A;
2) nano composite material described in claim 1 or 2 be scattered in to the organic solvent that can dissolve each other with water or obtain suspension-turbid liquid B the mixed liquor being formed by described organic solvent and water, by colloid liquid A described in step 1) and described suspension-turbid liquid B mix separated after, gained is deposited under inert atmosphere or reducing atmosphere or reduced pressure and is processed, obtain described nano-composite catalyst.
9. method according to claim 8, it is characterized in that: in the step 1) of described method one, soluble-salt or the transition metal in acid of described transition metal are selected from least one in Pt, Ru, Pd, Au, Rh, Ir, Cu and Os, preferably at least one in Pt, Ru, Pd, Rh and Ir; Described alcohol is all selected from the monohydric alcohol that the total number of carbon atoms is 1-8, the dihydroxylic alcohols that the total number of carbon atoms is 1-8, the trihydroxy alcohol that the total number of carbon atoms is 1-8, the monobasic methoxy or ethoxy derivative of the dihydroxylic alcohols that the total number of carbon atoms is 1-8, the monobasic methoxyl group of the trihydroxy alcohol that the total number of carbon atoms is 1-8 and at least one in ethyoxyl derivative; In the mixed liquor being comprised of described alcohol and water, the volumn concentration of water is 0.1-50%;
The concentration of the solution of described transistion metal compound is 0.01-100g/L, preferably 0.1-30g/L;
The step 2 of described method one), in, described reducing atmosphere is the atmosphere that contains hydrogen; Described inert atmosphere is selected from least one in nitrogen, argon gas and helium;
In described heating steps, temperature is 353-673K, preferred 373-573K, and the time is 0.5-100 hour;
Described organic solvent that can be miscible with water is selected from least one in methyl alcohol, ethanol, acetone, acetonitrile, dimethyl formamide and oxolane;
In the step 1) of described method two, soluble-salt or the transition metal in acid of described transition metal are selected from least one in Pt, Ru, Pd, Au, Rh, Ir, Cu and Os, preferably at least one in Pt, Ru, Pd, Rh and Ir; The concentration of the solution of described transistion metal compound is 0.01-100g/L, preferably 0.1-30g/L; In described heating steps, temperature is 373-473K, and the time is 0.5-100 hour;
The molar ratio of the alkali metal in the hydroxide of described alkali metal or alkaline-earth metal or alkaline-earth metal and described transition metal is 3-30;
Described alcohol is all selected from the monohydric alcohol that the total number of carbon atoms is 1-8, the dihydroxylic alcohols that the total number of carbon atoms is 1-8, the trihydroxy alcohol that the total number of carbon atoms is 1-8, the monobasic methoxy or ethoxy derivative of the dihydroxylic alcohols that the total number of carbon atoms is 1-8, the monobasic methoxyl group of the trihydroxy alcohol that the total number of carbon atoms is 1-8 and at least one in ethyoxyl derivative; In the mixed liquor being comprised of described alcohol and water, the volumn concentration of water is 0.1-50%;
The step 2 of described method two), in, described reducing atmosphere is the atmosphere that contains hydrogen; Described inert atmosphere is selected from least one in nitrogen, argon gas and helium; In described reduced pressure, vacuum degree is 10
3-10
5pa; In described treatment step, temperature is 298-1073K, preferred 353-773K, and the time is 0.5-100 hour;
Described in transition metal in described colloidal transition metal solution and claim 1 or 2, the mass ratio of nano composite material is 1:0.001-0.80;
Described organic solvent that can be miscible with water is selected from least one in methyl alcohol, ethanol, acetone, acetonitrile, dimethyl formamide and oxolane;
Described in described organic solvent and the mixed solvent that forms of water that can be miscible with water, the volumn concentration of water be 0.1-90%.
10. the application of the arbitrary described catalyst of claim 4-7 in preparing fuel cell.
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| CN111129513A (en) * | 2019-12-27 | 2020-05-08 | 大连理工大学 | Preparation method and application of nitrogen-doped carbon-supported low-platinum metal spherical nanoparticle electrocatalyst with uniform particle size |
| US11667530B1 (en) | 2022-03-09 | 2023-06-06 | Kunming University Of Science And Technology | Method for preparing heteroatom-doped CNHs and heteroatom-doped carbon nanohorns supporting platinum, and catalyst |
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