CN103657649B - A kind of prepare the carbon-supported nano platinum chromium intermetallic compound method as fuel battery cathode with proton exchange film catalyst - Google Patents
A kind of prepare the carbon-supported nano platinum chromium intermetallic compound method as fuel battery cathode with proton exchange film catalyst Download PDFInfo
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Abstract
The present invention relates to the energy, catalysis correlative technology field, particularly relate to a kind of carbon-supported nano platinum chromium intermetallic compound preparation method as fuel battery cathode with proton exchange film catalyst.The present invention provides a kind of and prepares carbon-supported nano platinum chromium intermetallic compound as the method for fuel battery cathode with proton exchange film catalyst based on metal carbonyl clusters approach, comprises the steps: the synthesis of (1) catalyst precursor metal carbonyl clusters；(2) injection of carbon carrier；(3) heat treatment of catalyst intermediate；(4) formation of intermetallic compound.Platinum Nanoparticles chromium intermetallic compound prepared by the method preparing carbon-supported nano platinum chromium intermetallic compound nanometer electrical catalyst based on metal carbonyl clusters approach provided by the present invention has features such as being evenly distributed, electrocatalytic oxidation reducing property high stability is good.
Description
Technical field
The present invention relates to the energy, catalysis correlative technology field, particularly relate to a kind of carbon-supported nano platinum chromium intermetallic compound preparation method as fuel battery cathode with proton exchange film catalyst.
Background technology
Proton Exchange Membrane Fuel Cells (includes DMFC) owing to having the advantages such as energy density height, the high and low pollution of energy conversion efficiency, operating temperature be low, becomes the study hotspot of new energy field.But, the energy conversion efficiency of current Proton Exchange Membrane Fuel Cells, cost, life-span etc. are not met by the demand of practical application, and it is the practical key of Proton Exchange Membrane Fuel Cells that exploitation has the eelctro-catalyst of high activity and stability.The current catalyst used in Proton Exchange Membrane Fuel Cells anode and cathode is all platino nanometer electrical catalyst, but feature that is high due to its cost and that easily poison limits its extensive use.
A lot of research work all has a superpower activity for preparation and stability takes into account the eelctro-catalyst of low cost, the especially research of electrocatalyst for cathode simultaneously.One of them important direction is the preparation of the nanometer electrical catalyst of platinum binary or ternary alloy three-partalloy (such as platinum-magnesium-yttrium-transition metal), and achieves good progress.Compared to Pt nano particle-M (M the is magnesium-yttrium-transition metal) catalyst of disordered structure, the Pt nano particle-M of ordered structure has higher active, better antitoxin voltinism energy and longer life-span and causes the concern of people.nullPlatinum Nanoparticles chromium disordered alloy (also known as: solid solution) eelctro-catalyst { Yang,H.,Alonso-Vante,N.,Lamy,C.,Akins,D.L.,2005.Highmethanoltoleranceofcarbon-supportedPt-Cralloynanoparticleelectrocatalystsforoxygenreduction.JElectrochemSoc152,A704-A709} due to have high oxidoreduction electro catalytic activity and in acid condition stable existence receive the parent of researcher and look at，But current most research work all focuses on the Platinum Nanoparticles evanohm catalyst with disordered structure，The platinum chromium intermetallic compound eelctro-catalyst of ordered structure is only had the report { Ghosh of minority,T.,Leonard,B.M.,Zhou,Q.,DiSalvo,F.J.,2010.PtAlloyandIntermetallicPhaseswithV,Cr,Mn,Ni,andCu:SynthesisAsNanomaterialsandPossibleApplicationsAsFuelCellCatalysts.ChemMater22,2190-2202.}.
Based on this, it is contemplated that design and develop the eelctro-catalyst of the fuel battery cathode with proton exchange film of a kind of platinum chromium bimetallic alloy with ordered structure by metal carbonyl clusters approach.By after Carbonyl Clusters load carbon material surface then through the eelctro-catalyst being thermally treated resulting in the carbon-supported nano platinum chromium intermetallic compound with high hydrogen reduction performance and high stability.
Summary of the invention
The shortcoming of prior art in view of the above, it is an object of the invention to provide and a kind of prepare carbon-supported nano platinum chromium intermetallic compound as the method for fuel battery cathode with proton exchange film catalyst based on metal carbonyl clusters approach, be used for solving the problems of the prior art.It is different from the method that metal carbonyl clusters approach prepares carbon-supported nano platino disordered alloy nanometer electrical catalyst, the present invention provides a kind of and prepares carbon-supported nano platinum chromium intermetallic compound (ordered alloy) method as fuel battery cathode with proton exchange film catalyst based on metal carbonyl clusters approach, including the synthesis of catalyst precursor metal carbonyl clusters, the injection of carbon carrier, the heat treatment of catalyst intermediate and catalyst post-processing step.Provided by the present invention a kind of prepare the carbon-supported nano platinum chromium intermetallic compound method as fuel battery cathode with proton exchange film catalyst based on metal carbonyl clusters approach, it is possible to prepare the carbon-supported nano platinum chromium intermetallic compound catalyst that size, pattern, composition are controlled.
For achieving the above object and other relevant purposes, first aspect present invention provides a kind of and prepares carbon-supported nano platinum chromium intermetallic compound as the method for fuel battery cathode with proton exchange film catalyst based on metal carbonyl clusters approach, comprises the steps:
(1) synthesis of catalyst precursor metal carbonyl clusters: weighing containing platinum compounds and dissolve in a solvent containing chromium compound, stirring is to being completely dissolved；Adding sodium acetate and sodium hydroxide in the solution be dissolved with metal ion, controlling solution is alkaline solution system；Passing into gas again in described alkaline solution and remove the air in this alkaline solution system, then reacting by heating under carbon monoxide atmosphere, obtains metal carbonyl clusters solution A；
(2) injection of carbon carrier: add carbon carrier in metal carbonyl clusters solution A；Heated and stirred, then removes solvent, obtains component B；
(3) heat treatment of catalyst intermediate: by component B heat treatment, obtains component C after cooling；
(4) formation of intermetallic compound: component C carries out heat treatment under pure hydrogen atmosphere, washes after cooling, obtains Platinum Nanoparticles chromium intermetallic compound catalyst after drying.
Preferably, in described step (1), containing platinum compounds with containing in chromium compound, the mol ratio of Pt:Cr is 1:0.25-3.
It is furthermore preferred that in described step (1), be selected from villaumite or the nitrate of platinum containing platinum compounds.
It is further preferred that in described step (1), be selected from the one in platinic sodium chloride, chloroplatinic acid, platinum chloride, platinum nitrate containing platinum compounds.
It is further preferred that described platinic sodium chloride is six water platinic sodium chlorides, described chloroplatinic acid is six water chloroplatinic acids.
It is furthermore preferred that in described step (1), be selected from the villaumite of chromium containing chromium compound.
It is further preferred that in described step (1), be selected from the one in chromium dichloride, chromium trichloride containing chromium compound.
It is further preferred that described chromium trichloride is chromic chloride hexahydrate.
Preferably, one or more the combination in described step (1), in solvent selected from methanol, ethanol, acetone, acetonitrile.
It is furthermore preferred that the described ratio containing platinum compounds with containing chromium compound quality sum with the addition of described solvent is g:ml=1:20-1000.
Preferably, in described step (1), mixing time is 2-10 minute.
Preferably, in described step (1), the addition of sodium acetate is with molar ratio computing, for 3-10 times of platinum element.
Preferably, in described step (1), the addition of sodium hydroxide is with molar ratio computing, for 0-5 times of platinum element.Sodium hydroxide purpose is in that to regulate pH with reaction speed.
Preferably, in described step (1), the pH value of alkaline solution system is 7.5 14.
Preferably, in described step (1), the gas passed in alkaline solution is a kind of in noble gas, CO (carbon monoxide converter) gas or their mixing.
Preferably, in described step (1), the actual conditions of reacting by heating is: react 2 hours-36 hours in 40-80 DEG C.
Preferably, in described step (2), when adding carbon carrier in metal carbonyl clusters solution A, adopt gas shield.
It is furthermore preferred that in described step (2), the gas that gas shield uses is a kind of in noble gas, carbon monoxide or their mixing.
Preferably, in described step (2), the addition of carbon carrier by quality ratio, for 0.3-5 times of platinum element.
It is furthermore preferred that in described step (2), carbon carrier one in activated carbon powder or order mesoporous carbon dust.
It is further preferred that in described step (2), the model of described activated carbon powder is the one in VXC-72, VXC-72R, KB-300, KB-600, AC-1 or AC-2.
Preferably, in described step (2), the actual conditions of heated and stirred is: stir 2-12 hour at 50 80 DEG C.
Preferably, in described step (2), the actual conditions removing solvent is: at 50 80 DEG C and under inert gas shielding.
Preferably, in described step (3), heat treatment carries out under gas shield.
It is furthermore preferred that in described step (3), the gas that gas shield uses is the mixing of hydrogen and noble gas.
It is further preferred that in described step (3), the gas that gas shield uses is 10v/v% hydrogen/noble gas gaseous mixture.
Preferably, in described step (3), heat treated actual conditions is: heat treatment 3-10 hour at 300-500 DEG C.
Preferably, in described step (4), heat treated actual conditions is: heat treatment 3-10 hour at 650-800 DEG C.
Preferably, in described step (4), the carbon load particle diameter of gained Platinum Nanoparticles chromium intermetallic compound catalyst is at 3-25nm.
It is furthermore preferred that in described step (1), (2), (3), a kind of in nitrogen or argon of noble gas or their mixing.
Second aspect present invention provides described and prepares the carbon-supported nano platinum chromium intermetallic compound method as fuel battery cathode with proton exchange film catalyst in the purposes of Proton Exchange Membrane Fuel Cells preparation field based on metal carbonyl clusters approach.
As mentioned above, it is desirable to provide a kind of method preparing carbon-supported nano platinum chromium intermetallic compound nanometer electrical catalyst based on metal carbonyl clusters approach, the Platinum Nanoparticles chromium intermetallic compound prepared by this preparation method has features such as being evenly distributed, electrocatalytic oxidation reducing property high stability is good.
Accompanying drawing explanation
The XRD figure of obtained carbon-supported nano platinum chromium intermetallic compound catalyst in Fig. 1 embodiment 1；
The TEM figure of obtained carbon-supported nano platinum chromium intermetallic compound catalyst in Fig. 2 embodiment 1；
In Fig. 3 embodiment 1, the hydrogen reduction performance test of obtained carbon-supported nano platinum chromium intermetallic compound and commercialization Pt/C (Alfa) catalyst is compared；
The pallium-on-carbon chromium intermetallic compound of indication hydrogen reduction Performance comparision before and after durability test in Fig. 4 embodiment 1.
Detailed description of the invention
Below by way of specific instantiation, embodiments of the present invention being described, those skilled in the art the content disclosed by this specification can understand other advantages and effect of the present invention easily.The present invention can also be carried out by additionally different detailed description of the invention or apply, and the every details in this specification based on different viewpoints and application, can also carry out various modification or change under the spirit without departing from the present invention.
It should be clear that the not concrete process equipment indicated or device all adopt the conventional equipment in this area or device in the following example；All force value and scope are all referring to absolute pressure.
Can also there is additive method step before and after described combination step in addition, it is to be understood that the one or more method steps mentioned in the present invention do not repel or additive method step can also be inserted between these steps specifically mentioned, except as otherwise noted；Will also be understood that, combination annexation between the one or more equipment/devices mentioned in the present invention is not repelled and can also be there are other equipment/devices before and after described unit equipment/device or can also insert other equipment/devices between these two equipment/devices specifically mentioned, except as otherwise noted.And, except as otherwise noted, the numbering of various method steps is only the convenient tool differentiating various method steps, but not for limiting the ordering of various method steps or limiting the enforceable scope of the present invention, the change of its relativeness or adjustment, when changing technology contents without essence, when being also considered as the enforceable category of the present invention.
Embodiment 1: the preparation of carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst
(1) the six water platinic sodium chloride (0.254mmol of 142.8mg are weighed, platinum element 49.53mg, molecular weight 561.87) and 22.8mg chromic chloride hexahydrate (0.086mmol, chromium element 4.47mg, molecular weight 266.45) it is dissolved in 45ml methanol, stir and within 2-10 minute, make it be completely dissolved；In the solution be dissolved with metal ion, add the sodium acetate of 168.2mg, regulate pH value of solution more than 7, it is thus achieved that alkaline solution system；In this alkaline solution, pass into CO (carbon monoxide converter) gas again remove the air in this alkaline solution system, then under carbon monoxide atmosphere in, 50 DEG C react 12 hours, obtain metal carbonyl clusters solution A；
(2) injection of carbon carrier: add the KB-600 of 217.8mg under nitrogen protection in metal carbonyl clusters solution A；Stir after 6 hours at 55 DEG C, then at 70 DEG C and remove solvent under nitrogen protection, obtain component B；
(3) heat treatment of catalyst intermediate: by component B under 10v/v% hydrogen/nitrogen mixture protection, heat treatment 3 hours at 500 DEG C, after cooling, obtain component C.
(4) by component C in a hydrogen atmosphere 800 DEG C process 3 hours, cooling, clean, dry obtain carbon-supported nano platinum chromium intermetallic compound.
The orderly platinum evanohm catalyst of carbon-supported nano obtained in embodiment 1 is characterized, the XRD figure of the orderly platinum chromium eelctro-catalyst of carbon-supported nano obtained and the TEM figure of platinum black nanometer electrical catalyst, respectively as depicted in figs. 1 and 2, known from Fig. 1 and Fig. 2: the platinum evanohm particle size of the carbon-supported nano platinum evanohm eelctro-catalyst of acquisition is about 8.2nm.
The carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst prepared in embodiment 1 and commercialization 20%Pt/C (Alfa) catalyst are carried out the comparison of hydrogen reduction performance:
The preparation of 1.1 test electrodes:
The water of carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst 10mg, 2.8ml of gained in embodiment 1 and Nafion (fromdupont) the solution ultrasonic disperse containing 5.3% of 0.2ml are configured to serosity in two hours, take wherein 3 microlitres to drop on the glass-carbon electrode of 3mm diameter cleaned in advance, make test electrode.
1.2 performance tests:
(1) electrode that the carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst in embodiment 1 is made is carried out hydrogen reduction performance test with 5mVs-1Scanning speed at the saturated 0.1MHClO of oxygen4In carry out, it is thus achieved that performance test collection of illustrative plates as shown in Figure 3, can learn from this collection of illustrative plates: obtained carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst hydrogen reduction performance be better than adopt commercialization Pt/C catalyst (Alfa).
(2) by the carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst in embodiment 1 at the saturated 0.1MHClO of nitrogen4With 50mVs in-0.24-0.76V (vsSCE) scope-1Scanning speed carry out durability test.Test result shows that the stability of obtained carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst is better than commercialization Pt/C catalyst (Alfa).
Embodiment 2: the preparation of carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst
(1) the six water platinic sodium chloride (0.254mmol of 142.8mg are weighed, platinum element 49.53mg, molecular weight 561.87) and 68.4mg chromic chloride hexahydrate (0.258mmol, chromium element 13.41mg, molecular weight 266.45) it is dissolved in 45ml methanol, stir and within 2-10 minute, make it be completely dissolved；In the solution be dissolved with metal ion, add the sodium acetate of 168.2mg, regulate pH value of solution more than 7, it is thus achieved that alkaline solution system；In this alkaline solution, pass into CO (carbon monoxide converter) gas again remove the air in this alkaline solution system, then under carbon monoxide atmosphere in, 50 DEG C react 12 hours, obtain metal carbonyl clusters solution A；
(2) injection of carbon carrier: add the KB-600 of 217.8mg under nitrogen protection in metal carbonyl clusters solution A；Stir after 6 hours at 55 DEG C, then at 70 DEG C and remove solvent under nitrogen protection, obtain component B；
(3) heat treatment of catalyst intermediate: by component B under 10v/v% hydrogen/nitrogen mixture protection, heat treatment 3 hours at 500 DEG C, after cooling, obtain component C.
(4) by component C in a hydrogen atmosphere 800 DEG C process 3 hours, cooling, clean, dry obtain carbon-supported nano platinum chromium intermetallic compound.
The carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst prepared in embodiment 2 and commercialization 20%Pt/C (Alfa) catalyst are carried out the comparison of hydrogen reduction performance:
The preparation of 2.1 test electrodes:
The water of carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst 10mg, 2.8ml of gained in embodiment 2 and Nafion (fromdupont) the solution ultrasonic disperse containing 5.3% of 0.2ml are configured to serosity in two hours, take wherein 3 microlitres to drop on the glass-carbon electrode of 3mm diameter cleaned in advance, make test electrode.
2.2 performance tests:
(1) electrode that the carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst in embodiment 2 is made is carried out hydrogen reduction performance test with 5mVs-1Scanning speed at the saturated 0.1MHClO of oxygen4In carry out, obtained carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst hydrogen reduction performance be better than adopt commercialization Pt/C catalyst (Alfa).
(2) by the carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst in embodiment 2 the saturated 0.1MHClO4 of nitrogen in-0.24-0.76V (vsSCE) scope with 50mVs-1Scanning speed carry out durability test.Test result shows that the stability of obtained carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst is better than commercialization Pt/C catalyst (Alfa).
Embodiment 3: the preparation of carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst
(1) the six water chloroplatinic acid (0.256mmol of 132.8mg are weighed, platinum element 49.92mg, molecular weight 517.92) and 22.8mg chromic chloride hexahydrate (0.086mmol, chromium element 4.47mg, molecular weight 266.45) it is dissolved in 45ml methanol, stir and within 2-10 minute, make it be completely dissolved；In the solution be dissolved with metal ion, add the sodium acetate of 168.2mg, regulate pH value of solution more than 7, it is thus achieved that alkaline solution system；In this alkaline solution, pass into CO (carbon monoxide converter) gas again remove the air in this alkaline solution system, then under carbon monoxide atmosphere in, 50 DEG C react 12 hours, obtain metal carbonyl clusters solution A；
(2) injection of carbon carrier: add the KB-600 of 217.8mg under nitrogen protection in metal carbonyl clusters solution A；Stir after 6 hours at 55 DEG C, then at 70 DEG C and remove solvent under nitrogen protection, obtain component B；
(3) heat treatment of catalyst intermediate: by component B under 10v/v% hydrogen/nitrogen mixture protection, heat treatment 3 hours at 500 DEG C, after cooling, obtain component C.
(4) by component C in a hydrogen atmosphere 800 DEG C process 3 hours, cooling, clean, dry obtain carbon-supported nano platinum chromium intermetallic compound.
The carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst prepared in embodiment 3 and commercialization 20%Pt/C (Alfa) catalyst are carried out the comparison of hydrogen reduction performance:
The preparation of 3.1 test electrodes:
The water of carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst 10mg, 2.8ml of gained in embodiment 3 and Nafion (fromdupont) the solution ultrasonic disperse containing 5.3% of 0.2ml are configured to serosity in two hours, take wherein 3 microlitres to drop on the glass-carbon electrode of 3mm diameter cleaned in advance, make test electrode.
3.2 performance tests:
(1) electrode that the carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst in embodiment 3 is made is carried out hydrogen reduction performance test with 5mVs-1Scanning speed at the saturated 0.1MHClO of oxygen4In carry out, obtained carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst hydrogen reduction performance be better than adopt commercialization Pt/C catalyst (Alfa).
(2) by the carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst in embodiment 3 the saturated 0.1MHClO4 of nitrogen in-0.24-0.76V (vsSCE) scope with 50mVs-1Scanning speed carry out durability test.Test result shows that the stability of obtained carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst is better than commercialization Pt/C catalyst (Alfa).
Embodiment 4: the preparation of carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst
(1) 142.8mg platinic sodium chloride (0.254mmol is weighed, platinum element 49.53mg, molecular weight 561.87) and the anhydrous chromium dichloride (0.086mmol of 10.5mg, chromium element 4.47mg, molecular weight 122.90) it is dissolved in 45ml methanol, stir and within 2-10 minute, make it be completely dissolved；In the solution be dissolved with metal ion, add the sodium acetate of 168.2mg, regulate pH value of solution more than 7, it is thus achieved that alkaline solution system；In this alkaline solution, pass into CO (carbon monoxide converter) gas again remove the air in this alkaline solution system, then under carbon monoxide atmosphere in, 50 DEG C react 12 hours, obtain metal carbonyl clusters solution A；
(2) injection of carbon carrier: add the VXC-72 carbon carrier of 217.8mg under nitrogen protection in metal carbonyl clusters solution A；Stir after 6 hours at 55 DEG C, then at 70 DEG C and remove solvent under nitrogen protection, obtain component B；
(3) heat treatment of catalyst intermediate: by component B under 10v/v% hydrogen/nitrogen mixture protection, heat treatment 3 hours at 500 DEG C, after cooling, obtain component C.
(4) by component C in a hydrogen atmosphere 800 DEG C process 3 hours, cooling, clean, dry obtain carbon-supported nano platinum chromium intermetallic compound.
The carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst prepared in embodiment 4 and commercialization 20%Pt/C (Alfa) catalyst are carried out the comparison of hydrogen reduction performance:
The preparation of 4.1 test electrodes:
The water of carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst 10mg, 2.8ml of gained in embodiment 5 and Nafion (fromdupont) the solution ultrasonic disperse containing 5.3% of 0.2ml are configured to serosity in two hours, take wherein 3 microlitres to drop on the glass-carbon electrode of 3mm diameter cleaned in advance, make test electrode.
4.2 performance tests:
(1) electrode that the carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst in embodiment 4 is made is carried out hydrogen reduction performance test with 5mVs-1Scanning speed at the saturated 0.1MHClO of oxygen4In carry out, it is thus achieved that performance test collection of illustrative plates as shown in Figure 3, can learn from this collection of illustrative plates: obtained carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst hydrogen reduction performance be better than adopt commercialization Pt/C catalyst (Alfa).
(2) by the carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst in embodiment 4 the saturated 0.1MHClO4 of nitrogen in-0.24-0.76V (vsSCE) scope with 50mVs-1Scanning speed carry out durability test.Test result shows that the stability of obtained carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst is better than commercialization Pt/C catalyst (Alfa).
Embodiment 5: carbon-supported nano platinum chromium intermetallic compound
(1) the six water platinic sodium chloride (0.254mmol of 142.8mg are weighed, platinum element 49.53mg, molecular weight 561.87) and 22.8mg chromic chloride hexahydrate (0.086mmol, chromium element 4.47mg, molecular weight 266.45) it is dissolved in 45ml ethanol, stir and within 2-10 minute, make it be completely dissolved；In the solution be dissolved with metal ion, add the sodium acetate of 168.2mg, regulate pH value of solution more than 7, it is thus achieved that alkaline solution system；In this alkaline solution, pass into CO (carbon monoxide converter) gas again remove the air in this alkaline solution system, then under carbon monoxide atmosphere in, 50 DEG C react 12 hours, obtain metal carbonyl clusters solution A；
(2) injection of carbon carrier: add the VXC-72 of 217.8mg under nitrogen protection in metal carbonyl clusters solution A；Stir after 6 hours at 55 DEG C, then at 70 DEG C and remove solvent under nitrogen protection, obtain component B；
(3) heat treatment of catalyst intermediate: by component B under 10v/v% hydrogen/nitrogen mixture protection, heat treatment 3 hours at 500 DEG C, after cooling, obtain component C.
(4) by component C in a hydrogen atmosphere 800 DEG C process 3 hours, cooling, clean, dry obtain carbon-supported nano platinum chromium intermetallic compound.
The orderly platinum evanohm catalyst of carbon-supported nano obtained in embodiment 5 is characterized, it is thus achieved that the platinum evanohm particle size of carbon-supported nano platinum evanohm eelctro-catalyst be about 16.2nm.
The carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst prepared in embodiment 5 and commercialization 20%Pt/C (Alfa) catalyst are carried out the comparison of hydrogen reduction performance:
The preparation of 1.1 test electrodes:
The water of carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst 10mg, 2.8ml of gained in embodiment 5 and Nafion (fromdupont) the solution ultrasonic disperse containing 5.3% of 0.2ml are configured to serosity in two hours, take wherein 3 microlitres to drop on the glass-carbon electrode of 3mm diameter cleaned in advance, make test electrode.
1.2 performance tests:
(1) electrode that the carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst in embodiment 5 is made is carried out hydrogen reduction performance test with 5mVs-1Scanning speed at the saturated 0.1MHClO of oxygen4In carry out, obtained carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst hydrogen reduction performance be better than adopt commercialization Pt/C catalyst (Alfa).
(2) by the carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst in embodiment 5 the saturated 0.1MHClO4 of nitrogen in-0.24-0.76V (vsSCE) scope with 50mVs-1Scanning speed carry out durability test.Test result shows that the stability of obtained carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst is better than commercialization Pt/C catalyst (Alfa).
Embodiment 6: carbon-supported nano platinum chromium intermetallic compound
(1) the six water chloroplatinic acid (0.276mmol of 142.8mg are weighed, platinum element 53.77mg, molecular weight 517.92) and 22.8mg chromic chloride hexahydrate (0.086mmol, chromium element 4.47mg, molecular weight 266.45) it is dissolved in 45ml methanol, stir and within 2-10 minute, make it be completely dissolved；In the solution be dissolved with metal ion, add the sodium acetate of 168.2mg and the sodium hydroxide of 30.8mg, regulate pH value of solution more than 7, it is thus achieved that alkaline solution system；In this alkaline solution, pass into CO (carbon monoxide converter) gas again remove the air in this alkaline solution system, then under carbon monoxide atmosphere in, 50 DEG C react 12 hours, obtain metal carbonyl clusters solution A；
(2) injection of carbon carrier: add the VXC-72 of 217.8mg under nitrogen protection in metal carbonyl clusters solution A；Stir after 6 hours at 55 DEG C, then at 70 DEG C and remove solvent under nitrogen protection, obtain component B；
(3) heat treatment of catalyst intermediate: by component B under 10% hydrogen/nitrogen mixture protection, heat treatment 3 hours at 500 DEG C, after cooling, obtain component C.
(4) by component C in a hydrogen atmosphere 800 DEG C process 3 hours, cooling, clean, dry obtain carbon-supported nano platinum chromium intermetallic compound.
The orderly platinum evanohm catalyst of carbon-supported nano obtained in embodiment 6 is characterized, it is thus achieved that the platinum evanohm particle size of carbon-supported nano platinum evanohm eelctro-catalyst be about 15.7nm.
The carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst prepared in embodiment 6 and commercialization 20%Pt/C (Alfa) catalyst are carried out the comparison of hydrogen reduction performance:
The preparation of 1.1 test electrodes:
The water of carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst 10mg, 2.8ml of gained in embodiment 6 and Nafion (fromdupont) the solution ultrasonic disperse containing 5.3% of 0.2ml are configured to serosity in two hours, take wherein 3 microlitres to drop on the glass-carbon electrode of 3mm diameter cleaned in advance, make test electrode.
1.2 performance tests:
(1) electrode that the carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst in embodiment 6 is made is carried out hydrogen reduction performance test with 5mVs-1Scanning speed at the saturated 0.1MHClO of oxygen4In carry out, obtained carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst hydrogen reduction performance be better than adopt commercialization Pt/C catalyst (Alfa).
(2) by the carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst in embodiment 6 the saturated 0.1MHClO4 of nitrogen in-0.24-0.76V (vsSCE) scope with 50mVs-1Scanning speed carry out durability test.Test result shows that the stability of obtained carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst is better than commercialization Pt/C catalyst (Alfa).
Embodiment 7: the preparation of carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst
(1) platinum chloride (0.254mmol of 85.6mg is weighed, platinum element 49.53mg, molecular weight 336.89) and 266.5mg chromic chloride hexahydrate (1mmol, chromium element 52mg, molecular weight 266.45) it is dissolved in 5ml acetone, stir and within 2-10 minute, make it be completely dissolved；In the solution be dissolved with metal ion, add the sodium acetate of 495.3mg and the sodium hydroxide of 247.7mg, regulate pH value of solution more than 7, it is thus achieved that alkaline solution system；In this alkaline solution, pass into CO (carbon monoxide converter) gas again remove the air in this alkaline solution system, then under carbon monoxide atmosphere in, 40 DEG C react 36 hours, obtain metal carbonyl clusters solution A；
(2) injection of carbon carrier: add the KB-300 of 14.86mg under nitrogen protection in metal carbonyl clusters solution A；Stir after 12 hours at 50 DEG C, then at 80 DEG C and remove solvent under nitrogen protection, obtain component B；
(3) heat treatment of catalyst intermediate: by component B under 10v/v% hydrogen/nitrogen mixture protection, heat treatment 10 hours at 300 DEG C, after cooling, obtain component C.
(4) by component C in a hydrogen atmosphere 650 DEG C process 10 hours, cooling, clean, dry obtain carbon-supported nano platinum chromium intermetallic compound.
The orderly platinum evanohm catalyst of carbon-supported nano obtained in embodiment 7 is characterized, it is thus achieved that the platinum evanohm particle size of carbon-supported nano platinum evanohm eelctro-catalyst be about 10nm.
The carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst prepared in embodiment 7 and commercialization 20%Pt/C (Alfa) catalyst are carried out the comparison of hydrogen reduction performance:
The preparation of 1.1 test electrodes:
The water of carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst 10mg, 2.8ml of gained in embodiment 7 and Nafion (fromdupont) the solution ultrasonic disperse containing 5.3% of 0.2ml are configured to serosity in two hours, take wherein 3 microlitres to drop on the glass-carbon electrode of 3mm diameter cleaned in advance, make test electrode.
1.2 performance tests:
(1) electrode that the carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst in embodiment 7 is made is carried out hydrogen reduction performance test with 5mVs-1Scanning speed at the saturated 0.1MHClO of oxygen4In carry out, obtained carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst hydrogen reduction performance be better than adopt commercialization Pt/C catalyst (Alfa).
(2) by the carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst in embodiment 7 the saturated 0.1MHClO4 of nitrogen in-0.24-0.76V (vsSCE) scope with 50mVs-1Scanning speed carry out durability test.Test result shows that the stability of obtained carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst is better than commercialization Pt/C catalyst (Alfa).
Embodiment 8: the preparation of carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst
(1) platinum nitrate (0.254mmol of 85.6mg is weighed, platinum element 49.53mg, molecular weight 319.09) and the anhydrous chromium dichloride (0.086mmol of 10.5mg, chromium element 4.47mg, molecular weight 122.90) it is dissolved in 100ml ethanol, stir and within 2-10 minute, make it be completely dissolved；In the solution be dissolved with metal ion, add the sodium acetate of 168.2mg and the sodium hydroxide of 30.8mg, regulate pH value of solution more than 7, it is thus achieved that alkaline solution system；In this alkaline solution, pass into nitrogen again remove the air in this alkaline solution system, then under carbon monoxide atmosphere in, 80 DEG C react 2 hours, obtain metal carbonyl clusters solution A；
(2) injection of carbon carrier: add the AC-1 of 247mg under nitrogen protection in metal carbonyl clusters solution A；Stir after 2 hours at 80 DEG C, then at 50 DEG C and remove solvent under nitrogen protection, obtain component B；
(3) heat treatment of catalyst intermediate: by component B under 10v/v% hydrogen/nitrogen mixture protection, heat treatment 10 hours at 300 DEG C, after cooling, obtain component C.
(4) by component C in a hydrogen atmosphere 650 DEG C process 10 hours, cooling, clean, dry obtain carbon-supported nano platinum chromium intermetallic compound.
The orderly platinum evanohm catalyst of carbon-supported nano obtained in embodiment 8 is characterized, it is thus achieved that the platinum evanohm particle size of carbon-supported nano platinum evanohm eelctro-catalyst be about 13nm.
The carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst prepared in embodiment 8 and commercialization 20%Pt/C (Alfa) catalyst are carried out the comparison of hydrogen reduction performance:
The preparation of 1.1 test electrodes:
The water of carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst 10mg, 2.8ml of gained in embodiment 8 and Nafion (fromdupont) the solution ultrasonic disperse containing 5.3% of 0.2ml are configured to serosity in two hours, take wherein 3 microlitres to drop on the glass-carbon electrode of 3mm diameter cleaned in advance, make test electrode.
1.2 performance tests:
(1) electrode that the carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst in embodiment 8 is made is carried out hydrogen reduction performance test with 5mVs-1Scanning speed at the saturated 0.1MHClO of oxygen4In carry out, obtained carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst hydrogen reduction performance be better than adopt commercialization Pt/C catalyst (Alfa).
(2) by the carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst in embodiment 8 the saturated 0.1MHClO4 of nitrogen in-0.24-0.76V (vsSCE) scope with 50mVs-1Scanning speed carry out durability test.Test result shows that the stability of obtained carbon-supported nano platinum chromium intermetallic compound eelctro-catalyst is better than commercialization Pt/C catalyst (Alfa).
In sum, the present invention effectively overcomes various shortcoming of the prior art and has high industrial utilization.
Above-described embodiment is illustrative principles of the invention and effect thereof only, not for the restriction present invention.Above-described embodiment all under the spirit and category of the present invention, can be modified or change by any those skilled in the art.Therefore, art has usually intellectual such as modifying without departing from all equivalences completed under disclosed spirit and technological thought or change, must be contained by the claim of the present invention.
Claims (12)
1. prepare carbon-supported nano platinum chromium intermetallic compound as a method for fuel battery cathode with proton exchange film catalyst based on metal carbonyl clusters approach, comprise the steps:
(1) synthesis of catalyst precursor metal carbonyl clusters: weighing containing platinum compounds and dissolve in a solvent containing chromium compound, described is 1:0.25-3 containing platinum compounds with containing the mol ratio of Pt:Cr in chromium compound, and stirring is to being completely dissolved；Adding sodium acetate and sodium hydroxide in the solution be dissolved with metal ion, the addition of sodium acetate is with molar ratio computing, and for 3-10 times of platinum element, the addition of sodium hydroxide is with molar ratio computing, and for 0-5 times of platinum element, controlling solution is alkaline solution system；In described alkaline solution, pass into gas again remove the air in this alkaline solution system, then in 40-80 DEG C of reacting by heating 2 hours-36 hours under carbon monoxide atmosphere, obtain metal carbonyl clusters solution A；
(2) injection of carbon carrier: in metal carbonyl clusters solution A add carbon carrier, the addition of carbon carrier by quality ratio, for 0.3-5 times of platinum element；At 50 80 DEG C heated and stirred 2-12 hour, then remove solvent, obtain component B；
(3) heat treatment of catalyst intermediate: by component B heat treatment 3-10 hour at 300-500 DEG C under gas shield, obtain component C after cooling；
(4) formation of intermetallic compound: by component C under pure hydrogen atmosphere at 650-800 DEG C heat treatment 3-10 hour, wash after cooling, obtain Platinum Nanoparticles chromium intermetallic compound catalyst after drying；
In described step (1), it is selected from the one in platinic sodium chloride, chloroplatinic acid, platinum chloride, platinum nitrate containing platinum compounds；
In described step (1), it is selected from the one in chromium dichloride, chromium trichloride containing chromium compound.
2. a kind of as claimed in claim 1 prepare the carbon-supported nano platinum chromium intermetallic compound method as fuel battery cathode with proton exchange film catalyst based on metal carbonyl clusters approach, it is characterized in that, one or more the combination in described solvent selected from methanol, ethanol, acetone, acetonitrile.
3. a kind of as claimed in claim 1 prepare the carbon-supported nano platinum chromium intermetallic compound method as fuel battery cathode with proton exchange film catalyst based on metal carbonyl clusters approach, it is characterized in that, in described step (1), the pH value of alkaline solution system is 7.5 14.
4. a kind of as claimed in claim 1 prepare the carbon-supported nano platinum chromium intermetallic compound method as fuel battery cathode with proton exchange film catalyst based on metal carbonyl clusters approach, it is characterized in that, in described step (1), the gas passed in alkaline solution is a kind of in noble gas, CO (carbon monoxide converter) gas or their mixing；Or, in described step (1), the gas passed in alkaline solution is a kind of in nitrogen, CO (carbon monoxide converter) gas or their mixing.
5. a kind of as claimed in claim 1 prepare the carbon-supported nano platinum chromium intermetallic compound method as fuel battery cathode with proton exchange film catalyst based on metal carbonyl clusters approach; it is characterized in that; in described step (2); when adding carbon carrier in metal carbonyl clusters solution A, adopt gas shield.
6. a kind of as claimed in claim 1 prepare the carbon-supported nano platinum chromium intermetallic compound method as fuel battery cathode with proton exchange film catalyst based on metal carbonyl clusters approach, it is characterized in that, in described step (2), carbon carrier one in activated carbon powder or order mesoporous carbon dust.
7. a kind of as claimed in claim 6 prepare the carbon-supported nano platinum chromium intermetallic compound method as fuel battery cathode with proton exchange film catalyst based on metal carbonyl clusters approach, it is characterized in that, in described step (2), the model of described activated carbon powder is the one in VXC-72, VXC-72R, KB-300, KB-600, AC-1 or AC-2.
8. a kind of as claimed in claim 1 prepare the carbon-supported nano platinum chromium intermetallic compound method as fuel battery cathode with proton exchange film catalyst based on metal carbonyl clusters approach; it is characterized in that; in described step (2), the actual conditions removing solvent is: at 50 80 DEG C and under inert gas shielding；Or, in described step (2), the actual conditions removing solvent is: at 50 80 DEG C and under nitrogen protection.
9. a kind of as claimed in claim 1 prepare the carbon-supported nano platinum chromium intermetallic compound method as fuel battery cathode with proton exchange film catalyst based on metal carbonyl clusters approach; it is characterized in that; in described step (3), the gas that gas shield uses is the mixing of hydrogen and noble gas；Or, in described step (3), the gas that gas shield uses is the mixing of hydrogen and nitrogen.
10. a kind of as claimed in claim 1 prepare the carbon-supported nano platinum chromium intermetallic compound method as fuel battery cathode with proton exchange film catalyst based on metal carbonyl clusters approach, it is characterized in that, in described step (4), the carbon load particle diameter of gained Platinum Nanoparticles chromium intermetallic compound catalyst is at 3-25nm.
11. a kind of as described in claim 4,8 or 9 prepares the carbon-supported nano platinum chromium intermetallic compound method as fuel battery cathode with proton exchange film catalyst based on metal carbonyl clusters approach, it is characterised in that described noble gas is selected from argon.
12. prepare the carbon-supported nano platinum chromium intermetallic compound method as fuel battery cathode with proton exchange film catalyst in the purposes of Proton Exchange Membrane Fuel Cells preparation field based on metal carbonyl clusters approach as described in claim 1-11 any claim.
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| CN105932308B (en) * | 2016-06-17 | 2018-03-30 | 宁波中科科创新能源科技有限公司 | The preparation method of nanometer electrical catalyst |
| CN109273730A (en) * | 2018-08-09 | 2019-01-25 | 浙江润涞科技服务有限公司 | A kind of preparation method of hydrogen cell electrode material |
| CN109706364B (en) * | 2019-02-21 | 2021-04-23 | 中国科学技术大学 | Intermetallic compound composite material, preparation method and application thereof |
| CN110600752B (en) * | 2019-09-18 | 2021-02-12 | 清华大学 | H2Method for preparing carbon-supported Pt alloy catalyst by gas-phase thermal reduction |
| CN110931816A (en) * | 2020-01-03 | 2020-03-27 | 宁波中科科创新能源科技有限公司 | Preparation method of nonmetal-stable supported platinum-based intermetallic compound |
| CN113368857B (en) * | 2021-04-29 | 2022-08-12 | 中国环境科学研究院 | Preparation method of bulk phase intermetallic compound supported catalyst |
| CN113594483B (en) * | 2021-07-28 | 2023-03-21 | 宁波中科科创新能源科技有限公司 | Preparation method of PtCo intermetallic compound catalyst and fuel cell |
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| CN115672321B (en) * | 2022-09-30 | 2024-01-02 | 哈尔滨工业大学（深圳） | Pt 3 Preparation method of Mn/CNTs catalyst and application of catalyst |
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