CN1933225A - PdP/C catalyst for high-performance direct methanoic acid fuel cell and producing method thereof - Google Patents
PdP/C catalyst for high-performance direct methanoic acid fuel cell and producing method thereof Download PDFInfo
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- CN1933225A CN1933225A CNA2006100861858A CN200610086185A CN1933225A CN 1933225 A CN1933225 A CN 1933225A CN A2006100861858 A CNA2006100861858 A CN A2006100861858A CN 200610086185 A CN200610086185 A CN 200610086185A CN 1933225 A CN1933225 A CN 1933225A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000000446 fuel Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims description 10
- 235000019253 formic acid Nutrition 0.000 title abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 61
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000008139 complexing agent Substances 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000003381 stabilizer Substances 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 18
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 101150003085 Pdcl gene Proteins 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000003610 charcoal Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 230000010355 oscillation Effects 0.000 claims description 12
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 206010013786 Dry skin Diseases 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002250 absorbent Substances 0.000 claims description 8
- 230000002745 absorbent Effects 0.000 claims description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 8
- 239000011698 potassium fluoride Substances 0.000 claims description 6
- 235000013024 sodium fluoride Nutrition 0.000 claims description 6
- 239000011775 sodium fluoride Substances 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
- 235000003270 potassium fluoride Nutrition 0.000 claims description 4
- 238000012958 reprocessing Methods 0.000 claims description 4
- 239000004328 sodium tetraborate Substances 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract description 13
- 229910002666 PdCl2 Inorganic materials 0.000 abstract 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 abstract 2
- 229910003953 H3PO2 Inorganic materials 0.000 abstract 1
- 229910021205 NaH2PO2 Inorganic materials 0.000 abstract 1
- 229910001382 calcium hypophosphite Inorganic materials 0.000 abstract 1
- 229910052755 nonmetal Inorganic materials 0.000 abstract 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 abstract 1
- 229910001380 potassium hypophosphite Inorganic materials 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 17
- 150000002500 ions Chemical class 0.000 description 7
- 238000002604 ultrasonography Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 231100000740 envenomation Toxicity 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000007785 strong electrolyte Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
This invention relates to a PdP/C catalyst of a high performance direct formic acid fuel battery including: loading Pd particles onto a carbon carrier, in which, the Pd particle is 1-80% that of the carbon carrier mass and the diameter is 3.0nm and contains a non-metal element P, the atomic ration of Pd and P is 8-12:1. The preparation method includes: adding a complexing agent, a stabilizing agent, PdCl2 and active carbon carrier to be oscillated with supersonic to get a component to be added by excessive reducer slowly, and the PdCl2 reacts with the reducer fully and P is introduced so that the recovered PdP particles are adsorbed on the carbon carrier to get component B, in which, introduction of P applies the following one or many reducers: H3PO2, KH2PO2, NaH2PO2 and Ca(H2PO2)2, the mol ratio of Pd and the reducer is 1:4-30, washing component B to be dried under vacuum or inert gas.
Description
Technical field
The present invention relates to a kind of catalyst, be specifically related to the PdP/C catalyst of the direct aminic acid fuel battery of a kind of high-performance---carbon carries ultra-fine PdP catalyst; And should---carbon carries ultra-fine PdP Preparation of catalysts method.
Background technology
In recent years, direct methanol fuel cell (DMFC) development in recent years is rapid, methyl alcohol at room temperature acts as a fuel and has high-energy-density, but because methyl alcohol is made fuel and is still had many technical problems, poisonous inflammable as methyl alcohol, methyl alcohol can see through the Nafion barrier film and arrive cathode chamber and oxidation etc. takes place on negative electrode.
People attempt to seek and have more potential alternative fuel and replace methyl alcohol, and the liquid formic acid solution is a kind of liquid fuel with potential attraction.Formic acid has the following advantages than methyl alcohol: at first, formic acid is a kind of strong electrolyte, helps increasing electronics, proton and CO in the anode chamber
2Conduction; Secondly, compare with methyl alcohol, formic acid is nontoxic; The 3rd, the electrochemistry oxidation performance of formic acid is better than methyl alcohol, and the theoretical open circuit voltage that the calculating by Gibbs free energy can get aminic acid fuel battery is 1.45V, than methyl alcohol height; The 4th, the formic acid electroxidation can reduce the formation of envenomation intermediate product by dual path; The 5th owing between the formic acid anion that sulfonic acid group in the Nafion film and formic acid partly decompose generation repulsive interaction is arranged, therefore, formic acid to the permeability of Nafion film much smaller than methyl alcohol; Nonflammable in addition simultaneously, but advantages such as high concentration use more and more receive numerous researchers' concern.
Pd metal pair formic acid has unique catalytic oxidation activity.But the average grain diameter of the Pd catalyst particle that conventional liquid-phase reduction method makes is bigger, and single Pd metallic catalyst is very unstable, easy oxidized inactivation, the Pd that therefore presses for preparation small particle diameter, high activity and stability is catalyst based, improves the utilance of Pd catalyst.Therefore, exploring the method that can be used for the preparation of industrialization high performance catalyst is a problem that makes concern.
For the Pd catalyst, general preparation method can not overcome the shortcoming of Pd particle oxidation inactivation, and is difficult to make the less Pd catalyst of particle diameter, and simultaneously the pure Pd catalyst that particle diameter is more little is easy more oxidized and lose activity in air.
Summary of the invention
The PdP/C catalyst that the purpose of this invention is to provide a kind of small particle diameter of neomorph, high performance direct aminic acid fuel battery---carbon carries ultra-fine PdP catalyst, and this catalyst can present very high catalytic activity and stability to the electrochemical oxidation of formic acid.Second purpose of the present invention provides this carbon and carries ultra-fine PdP Preparation of catalysts method.
The technical scheme of finishing the foregoing invention task is:
The PdP/C catalyst of the direct aminic acid fuel battery of high-performance, it consists of: the Pd metallic is carried on the charcoal carrier, and the Pd metallic accounts for 1～80% of charcoal carrier quality, and the particle diameter of Pd is 3.0nm; Contain nonmetalloid P simultaneously, wherein the atomic ratio of Pd and P is 8～12: 1.
Furtherly, the PdP/C catalyst of the direct aminic acid fuel battery of high-performance of the present invention is the catalyst that obtains by following preparation process: add complexing agent, stabilizer and PdCl in water
2Weak solution adds absorbent charcoal carrier, and sonic oscillation gets component A---the suspension-turbid liquid of active carbon; Wherein the amount of Pd metal adding accounts for 1～80% of charcoal carrier quality;
In component A, slowly add excessive reductant, make PdCl
2With reducing agent fully reaction takes place, and introduce element P, thereby the PdP particulate that restores is adsorbed on the carbon carrier, get B component, wherein one or more in the following reducing agent: H is adopted in the introducing of P
3PO
2, KH
2PO
2, NaH
2PO
2, Ca (H
2PO
2)
2The mol ratio of Pd and described reducing agent 1: 4～30;
Washing component B, vacuum or inert gas shielding are dry down.
More optimize and more particularly, PdP/C catalyst of the present invention is the catalyst that obtains by following preparation process:
The injection of catalyst precursor: add 0.0228～45.2mmoL complexing agent and 0.0452～33.9mmoL stabilizer and 5.7 * 10 at 10mL water
-3～2.26mmoL PdCl
2Weak solution adds the 60mg absorbent charcoal carrier, and sonic oscillation gets component A, the suspension-turbid liquid of active carbon; Wherein the amount of Pd metal adding accounts for 1～80% of charcoal carrier quality.
The low temperature liquid phase reduction: component A slowly adds 0.0228～67.8mmoL reducing agent under 15～90 ℃ of conditions, described reducing agent is selected from: H
3PO
2, KH
2PO
2, NaH
2PO
2, Ca (H
2PO
2)
2In one or more; Sonic oscillation (or stirring) 0.5～6 hour makes PdCl
2With reducing agent fully reaction taking place, thereby the PdP particulate that restores is adsorbed on the carbon carrier, gets B component.
The reprocessing part: 2 B component that obtain are washed with water repeatedly, and 60 ℃ of dryings of vacuum (or nitrogen protection) promptly make the carrier loaded PdP/C catalyst of charcoal, and wherein the particle size of noble metal is 3.0nm.
Described complexing agent is a kind of in ammonium fluoride, sodium fluoride, the potassium fluoride, and the mol ratio of described Pd and described complexing agent is 1: 4～20;
Described stabilizer is a kind of in boric acid or the borax, the mol ratio of Pd and described stabilizer 1: 8～15.
The scheme of finishing second invention task is: the direct aminic acid fuel battery PdP/C of high stability Preparation of catalysts method, and step is as follows,
In water, add complexing agent, stabilizer and PdCl
2Weak solution adds absorbent charcoal carrier, and sonic oscillation gets component A---the suspension-turbid liquid of active carbon; Wherein the amount of Pd metal adding accounts for 1～80% of charcoal carrier quality;
In component A, slowly add excessive reductant, make PdCl
2With reducing agent fully reaction takes place, and introduce element P, thereby the PdP particulate that restores is adsorbed on the carbon carrier, get B component, wherein one or more in the following reducing agent: H is adopted in the introducing of P
3PO
2, KH
2PO
2, NaH
2PO
2, Ca (H
2PO
2)
2The mol ratio of Pd and described Pd and reducing agent 1: 4～30;
Washing component B, vacuum or inert gas shielding are dry down.
More optimize and more particularly, preparation method's of the present invention step is:
The injection of catalyst precursor: add 0.0228～45.2mmoL complexing agent and 0.0452～33.9mmoL stabilizer and 5.7 * 10 at 10mL water
-3～2.26mmoL PdCl
2Weak solution adds the 60mg absorbent charcoal carrier, and sonic oscillation gets component A, the suspension-turbid liquid of active carbon; Wherein the amount of Pd metal adding accounts for 1～80% of charcoal carrier quality.
The low temperature liquid phase reduction: component A slowly adds 0.0228～67.8mmoL reducing agent under 15～90 ℃ of conditions, described reducing agent is selected from: H
3PO
2, KH
2PO
2, NaH
2PO
2, Ca (H
2PO
2)
2In one or more; Sonic oscillation (or stirring) 0.5～6 hour makes PdCl
2With reducing agent fully reaction taking place, thereby the PdP particulate that restores is adsorbed on the carbon carrier, gets B component.
The reprocessing part: 2 B component that obtain are washed with water repeatedly, and 60 ℃ of dryings of vacuum (or nitrogen protection) promptly make the carrier loaded PdP/C catalyst of charcoal, and wherein the particle size of noble metal is 3.0nm.
Complexing agent described in the above scheme is a kind of in ammonium fluoride, sodium fluoride, the potassium fluoride; Stabilizer is a kind of in boric acid or the borax.
In the mol ratio 1: 4～20 of the Pd described in the preparation process and described Pd and complexing agent, optimal values is 1: 5.
In the mol ratio 1: 8～15 of the Pd described in the preparation process and described Pd and stabilizer, optimal values is 1: 10.
In the mol ratio 1: 4～30 of the Pd described in the preparation process and described Pd and reducing agent agent, optimal values is 1: 8.
Experimental result shows: in the PdP/C catalyst for preparing, and the about 3.0nm of the average grain diameter of Pd particle.The catalyst P dP/C that particle size is suitable shows very excellent electro catalytic activity and stability than Pd/C.By the introducing of nonmetalloid P, improved the stability of this catalyst.
Description of drawings
Fig. 1: the energy scatter spectra (EDS) of 20% PdP/C catalyst;
Fig. 2: the PdP/C catalyst TEM photo that makes.PdP metallic average grain diameter 3.0nm, and particle has good decentralization and excellent homogeneity.
Fig. 3: under same system, utilize NaH
2PO
2(curve a) and traditional NaBH for the PdP/C catalyst that makes as reducing agent
4The Pd/C catalyst that reducing agent makes (curve b) is at 0.5mol/LHCOOH+0.5mol/L H
2SO
4Cyclic voltammogram in the solution.Use NaH
2PO
2The spike potential of the PdP/C catalyst that reduction makes is than the negative 8mV that moved of pure Pd/C.And peak current is also obviously different, and the PdP/C catalyst is obviously higher to the electro catalytic activity of formic acid;
Fig. 4: under same system, utilize NaH
2PO
2(curve a) and traditional NaBH for the PdP/C catalyst that makes as reducing agent
4The Pd/C catalyst that reducing agent makes (curve b) is at 0.5mol/LHCOOH+0.5mol/L H
2SO
4Timing current curve in the solution.As seen from Figure 4, the PdP/C catalyst is better than common Pd/C stability.
Embodiment
Embodiment 1:
Get 10ml water, add 31mgNaF and 125mgH
3BO
3, add 3.13ml 0.04504molL
-1PdCl
2The aqueous solution behind the ultrasonic 10min, adds the 60mg active carbon, continues ultrasonic 30min, makes PdCl
2With the suspension-turbid liquid of active carbon, transferring pH with ammoniacal liquor is 8～9.
Get 10ml water, add 0.0228mmol NaH
2PO
2, under ultrasound condition with above-mentioned PdCl
2Slowly be added drop-wise to NaH with the suspension-turbid liquid of active carbon
2PO
2In the aqueous solution, continued ultrasonic 1 hour, stirred 6 hours down, make PdCl in 90 ℃ of water-baths
2With reducing agent NaH
2PO
2Complete reaction.
Repeatedly remove foreign ion with secondary water washing, promptly to make Pd metal carrying capacity be 20% PdP/C fine catalyst for 60 ℃ of dryings under vacuum condition.
With reference to Fig. 1～Fig. 4:
Fig. 1: the energy scatter spectra (EDS) of 20% PdP/C catalyst;
Fig. 2: the PdP/C catalyst TEM photo that makes.PdP metallic average grain diameter 3.0nm, and particle has good decentralization and excellent homogeneity.
Fig. 3: under same system, utilize NaH
2PO
2(curve a) and traditional NaBH for the PdP/C catalyst that makes as reducing agent
4The Pd/C catalyst that reducing agent makes (curve b) is at 0.5mol/LHCOOH+0.5mol/L H
2SO
4Cyclic voltammogram in the solution.Use NaH
2PO
2The spike potential of the PdP/C catalyst that reduction makes is than the negative 8mV that moved of pure Pd/C.And peak current is also obviously different, and the PdP/C catalyst is obviously higher to the electro catalytic activity of formic acid;
Fig. 4: under same system, utilize NaH
2PO
2(curve a) and traditional NaBH for the PdP/C catalyst that makes as reducing agent
4The Pd/C catalyst that reducing agent makes (curve b) is at 0.5mol/LHCOOH+0.5mol/L H
2SO
4Timing current curve in the solution.As seen from Figure 4, the PdP/C catalyst is better than common Pd/C stability.
10ml water adds 25mg NH
4F and 125mg H
3BO
3, add 5.37ml 0.04504molL
-1PdCl
2The aqueous solution behind the ultrasonic 10min, adds the 60mg active carbon, continues ultrasonic 30min, makes PdCl
2Suspension-turbid liquid with active carbon.
Get 10ml water, add 2mmol NaH
2PO
2With 2mmol H
3PO
2, under ultrasound condition with above-mentioned PdCl
2Slowly be added drop-wise in the reducing agent aqueous solution with the suspension-turbid liquid of active carbon, continued ultrasonic 1 hour, stirred 6 hours down, make PdCl in 90 ℃ of water-baths
2With the reducing agent complete reaction.Be cooled to filtering and washing after the room temperature, repeatedly remove foreign ion with secondary water washing, at N
2It is the 30%PdP/C fine catalyst that the following 60 ℃ of dryings of gas shiled promptly make Pd metal carrying capacity.
Embodiment 3
10ml water adds 44mg KF and 125mg H
3BO
3, add 8.37ml 0.04504molL
-1PdCl
2The aqueous solution behind the ultrasonic 10min, adds the 60mg active carbon, continues ultrasonic 30min, makes PdCl
2Suspension-turbid liquid with active carbon.
Get 10ml water, add 3mmol NaH
2PO
2, 3mmol H
3PO
2, 3mmol KH
2PO
2, under ultrasound condition with above-mentioned PdCl
2Slowly be added drop-wise in the reducing agent aqueous solution with the suspension-turbid liquid of active carbon, continued ultrasonic 1 hour, stirred 6 hours down, make PdCl in 90 ℃ of water-baths
2With the reducing agent complete reaction.Be cooled to filtering and washing after the room temperature, repeatedly remove foreign ion with secondary water washing, promptly to make Pd metal carrying capacity be 40% PdP/C fine catalyst for 60 ℃ of dryings under vacuum condition.
Embodiment 4
10ml water adds 44mg KF and 186mg Na
2B
4O
710H
2O adds 12.5ml 0.04504molL
-1PdCl
2The aqueous solution behind the ultrasonic 10min, adds the 60mg active carbon, continues ultrasonic 30min, makes PdCl
2Suspension-turbid liquid with active carbon.
Get 10ml water, add 5mmol NaH
2PO
2, 5mmol H
3PO
2, 5mmol KH
2PO
2, 5mmolCa (H
2PO
2)
2, under ultrasound condition with above-mentioned PdCl
2Slowly be added drop-wise in the reducing agent aqueous solution with the suspension-turbid liquid of active carbon, continued ultrasonic 1 hour, stirred 6 hours down, make PdCl in 90 ℃ of water-baths
2With the reducing agent complete reaction.Be cooled to filtering and washing after the room temperature, repeatedly remove foreign ion with secondary water washing, at N
2It is 50% PdP/C fine catalyst that the following 60 ℃ of dryings of gas shiled promptly make Pd metal carrying capacity.
10ml water adds 25mg NH
4F and 186mg Na
2B
4O
710H
2O adds 18.8ml0.04504molL
-1PdCl
2The aqueous solution behind the ultrasonic 10min, adds the 60mg active carbon, continues ultrasonic 30min, makes PdCl
2Suspension-turbid liquid with active carbon.
Get 10ml water, add 20mmol H
3PO
2, under ultrasound condition with above-mentioned PdCl
2Slowly be added drop-wise in the reducing agent aqueous solution with the suspension-turbid liquid of active carbon, continued ultrasonic 1 hour, stirred 6 hours down, make PdCl in 90 ℃ of water-baths
2With the reducing agent complete reaction.Be cooled to filtering and washing after the room temperature, repeatedly remove foreign ion with secondary water washing, promptly to make Pd metal carrying capacity be 60% PdP/C fine catalyst for 60 ℃ of dryings under vacuum condition.
10ml water adds 31mg NaF and 186mg Na
2B
4O
710H
2O adds 29.2ml0.04504molL
-1PdCl
2The aqueous solution behind the ultrasonic 10min, adds the 60mg active carbon, continues ultrasonic 30min, makes PdCl
2Suspension-turbid liquid with active carbon.
Get 10ml water, add 40mmol KH
2PO
2, under ultrasound condition with above-mentioned PdCl
2Slowly be added drop-wise in the reducing agent aqueous solution with the suspension-turbid liquid of active carbon, continued ultrasonic 1 hour, stirred 6 hours down, make PdCl in 90 ℃ of water-baths
2With the reducing agent complete reaction.Be cooled to filtering and washing after the room temperature, repeatedly remove foreign ion with secondary water washing, at N
2It is 70% PdP/C fine catalyst that the following 60 ℃ of dryings of gas shiled promptly make Pd metal carrying capacity.
Embodiment 7, and is substantially the same manner as Example 1, but following difference is arranged:
Complexing agent is selected NH for use
4F; Stabilizer still is H
3BO
3Pd is 1: 2 with the ratio of the amount of complexing agent; Reducing agent is selected Ca (H for use
2PO
2)
2Add 0.13ml 0.04504molL
-1PdCl
2The aqueous solution; The amount that the Pd metal adds in the catalyst that obtains accounts for 1% of charcoal carrier amount.
Embodiment 8,
10ml water adds 31mg NaF and 186mg Na
2B
4O
710H
2O adds 50.1ml0.04504molL
-1PdCl
2The aqueous solution behind the ultrasonic 10min, adds the 60mg active carbon, continues ultrasonic 30min, makes PdCl
2Suspension-turbid liquid with active carbon.
Get 10ml water, add 67.8mmol NaH
2PO
2, under ultrasound condition with above-mentioned PdCl
2Slowly be added drop-wise in the reducing agent aqueous solution with the suspension-turbid liquid of active carbon, continued ultrasonic 1 hour, stirred 6 hours down, make PdCl in 90 ℃ of water-baths
2With the reducing agent complete reaction.Be cooled to filtering and washing after the room temperature, repeatedly remove foreign ion with secondary water washing, at N
2It is 80% PdP/C fine catalyst that the following 60 ℃ of dryings of gas shiled promptly make Pd metal carrying capacity.
Embodiment 9, and is substantially the same manner as Example 1, but following difference is arranged:
Reducing agent is selected H for use
3PO
2And KH
2PO
2The composite reduction system; Add 0.66ml 0.04504molL
-1PdCl
2The aqueous solution; The amount that the Pd metal adds in the catalyst that obtains accounts for 5% of charcoal carrier amount.
Reducing agent is selected H for use
3PO
2And Ca (H
2PO
2)
2The composite reduction system; Add 29.2ml 0.04504molL
-1PdCl
2The aqueous solution, the amount that the Pd metal adds in the catalyst of acquisition accounts for 70% of charcoal carrier amount.
Embodiment 11～16, and is basic identical with embodiment 1～10, but following difference is arranged respectively:
Described reducing agent adopts KH respectively
2PO
2+ Ca (H
2PO
2)
2, KH
2PO
2+ NaH
2PO
2, NaH
2PO
2+ Ca (H
2PO
2)
2, H
3PO
2+ NaH
2PO
2+ Ca (H
2PO
2)
2, H
3PO
2+ KH
2PO
2+ Ca (H
2PO
2)
2, KH
2PO
2+ NaH
2PO
2+ Ca (H
2PO
2)
2The composite reduction system.
Embodiment 17,18, and is basic identical with embodiment 1～10, but described reducing agent adopts KH respectively separately
2PO
2, Ca (H
2PO
2)
2
Claims (8)
1, the PdP/C catalyst of the direct aminic acid fuel battery of high-performance, it consists of: the Pd metallic is carried on the charcoal carrier, and the Pd metallic accounts for 1～80% of charcoal carrier quality, and the particle diameter of Pd is 3.0nm; Contain nonmetalloid P simultaneously, wherein the atomic ratio of Pd and P is 8～12: 1.
2, according to the PdP/C catalyst of the direct aminic acid fuel battery of the described high-performance of claim 1, it is characterized in that, the PdP/C catalyst of the direct aminic acid fuel battery of described high-performance is the catalyst that obtains by following preparation process: add complexing agent, stabilizer and PdCl in water
2Weak solution adds absorbent charcoal carrier, and sonic oscillation gets component A---the suspension-turbid liquid of active carbon; Wherein the amount of Pd metal adding accounts for 1～80% of charcoal carrier quality;
In component A, slowly add excessive reductant, make PdCl
2With reducing agent fully reaction takes place, and introduce element P, thereby the PdP particulate that restores is adsorbed on the carbon carrier, get B component, wherein one or more in the following reducing agent: H is adopted in the introducing of P
3PO
2, KH
2PO
2, NaH
2PO
2, Ca (H
2PO
2)
2The mol ratio of described Pd and reducing agent is 1: 4～30;
Washing component B, vacuum or inert gas shielding are dry down.
According to the PdP/C catalyst of the direct aminic acid fuel battery of the described high-performance of claim 2, it is characterized in that 3, described PdP/C catalyst is the catalyst that obtains by following preparation process:
The injection of catalyst precursor: add 0.0228～45.2mmoL complexing agent and 0.0452～33.9mmoL stabilizer and 5.7 * 10 at 10mL water
-3～2.26mmoL PdCl
2Weak solution adds the 60mg absorbent charcoal carrier, and sonic oscillation gets component A, the suspension-turbid liquid of active carbon; Wherein the amount of Pd metal adding accounts for 1～80% of charcoal carrier quality;
The low temperature liquid phase reduction: component A slowly adds 0.0228～67.8mmoL reducing agent under 15～90 ℃ of conditions, described reducing agent is selected from: H
3PO
2, KH
2PO
2, NaH
2PO
2, Ca (H
2PO
2)
2In one or more; Sonic oscillation or stirred 0.5～6 hour makes PdCl
2With reducing agent fully reaction taking place, thereby the PdP particulate that restores is adsorbed on the carbon carrier, gets B component;
The reprocessing part: 2 B component that obtain are washed with water repeatedly, and 60 ℃ of dryings of vacuum or nitrogen protection promptly make the carrier loaded PdP/C catalyst of charcoal, and wherein the particle size of noble metal is 3.0nm.
4, according to the PdP/C catalyst of claim 2 or the direct aminic acid fuel battery of 3 described high-performance, it is characterized in that:
Described complexing agent is a kind of in ammonium fluoride, sodium fluoride, the potassium fluoride, and the mol ratio of described Pd and described complexing agent is 1: 4～20; Described stabilizer is a kind of in boric acid or the borax, and the mol ratio of described Pd and stabilizer is 1: 8～15.
5, the PdP/C Preparation of catalysts method of the direct aminic acid fuel battery of the described high-performance of a kind of claim 1, step is as follows,
In water, add complexing agent, stabilizer and PdCl
2Weak solution adds absorbent charcoal carrier, and sonic oscillation gets component A---the suspension-turbid liquid of active carbon; Wherein the amount of Pd metal adding accounts for 1～80% of charcoal carrier quality;
In component A, slowly add excessive reductant, make PdCl
2With reducing agent fully reaction takes place, and introduce element P, thereby the PdP particulate that restores is adsorbed on the carbon carrier, get B component, wherein one or more in the following reducing agent: H is adopted in the introducing of P
3PO
2, KH
2PO
2, NaH
2PO
2, Ca (H
2PO
2)
2The mol ratio of described Pd and reducing agent 1: 4～30;
Washing component B, vacuum or inert gas shielding are dry down.
6, according to the PdP/C Preparation of catalysts method of the direct aminic acid fuel battery of the described high-performance of claim 5, it is characterized in that concrete steps are:
The injection of catalyst precursor: add 0.0228～45.2mmoL complexing agent and 0.0452～33.9mmoL stabilizer and 5.7 * 10 at 10mL water
-3～2.26mmoL PdCl
2Weak solution adds the 60mg absorbent charcoal carrier, and sonic oscillation gets component A, the suspension-turbid liquid of active carbon; Wherein the amount of Pd metal adding accounts for 1～80% of charcoal carrier quality;
The low temperature liquid phase reduction: component A slowly adds 0.0228～67.8mmoL reducing agent under 15～90 ℃ of conditions, described reducing agent is selected from: H
3PO
2, KH
2PO
2, NaH
2PO
2, Ca (H
2PO
2)
2In one or more; Sonic oscillation or stirred 0.5～6 hour makes PdCl
2With reducing agent fully reaction taking place, thereby the PdP particulate that restores is adsorbed on the carbon carrier, gets B component;
The reprocessing part: 2 B component that obtain are washed with water repeatedly, and vacuum or nitrogen protection 60C drying promptly make the carrier loaded PdP/C catalyst of charcoal, and wherein the particle size of noble metal is 3.0nm.
7, according to the PdP/C Preparation of catalysts method of claim 5 or the direct aminic acid fuel battery of 6 described high-performance, it is characterized in that,
Described complexing agent is a kind of in ammonium fluoride, sodium fluoride, the potassium fluoride;
Stabilizer is a kind of in boric acid or the borax;
The mol ratio of described Pd and described complexing agent is 1: 4～20;
The mol ratio of described Pd and described stabilizer is 1: 8～15;
The mol ratio of described Pd and described reducing agent agent is 1: 4～30.
8, according to the PdP/C Preparation of catalysts method of the direct aminic acid fuel battery of the described high-performance of claim 7, it is characterized in that,
The mol ratio of described Pd and described complexing agent is 1: 5;
The mol ratio of described Pd and described stabilizer is 1: 10;
The mol ratio of described Pd and described reducing agent agent is 1: 8.
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| CNA2006100861858A CN1933225A (en) | 2006-09-08 | 2006-09-08 | PdP/C catalyst for high-performance direct methanoic acid fuel cell and producing method thereof |
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| CNA2006100861858A CN1933225A (en) | 2006-09-08 | 2006-09-08 | PdP/C catalyst for high-performance direct methanoic acid fuel cell and producing method thereof |
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| CN102078816A (en) * | 2010-12-23 | 2011-06-01 | 西北师范大学 | Selenium/carbon compound material, preparation of selenium/carbon compound material and application of selenium/carbon compound material in fuel-cell catalyst preparation |
| WO2012004639A1 (en) | 2010-07-09 | 2012-01-12 | Universidade De Trás-Os-Montes E Alto Douro | Palladium alloy catalysts for fuel cell cathodes and a method of preparing the same |
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- 2006-09-08 CN CNA2006100861858A patent/CN1933225A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012004639A1 (en) | 2010-07-09 | 2012-01-12 | Universidade De Trás-Os-Montes E Alto Douro | Palladium alloy catalysts for fuel cell cathodes and a method of preparing the same |
| CN102078816A (en) * | 2010-12-23 | 2011-06-01 | 西北师范大学 | Selenium/carbon compound material, preparation of selenium/carbon compound material and application of selenium/carbon compound material in fuel-cell catalyst preparation |
| CN108236951A (en) * | 2016-12-26 | 2018-07-03 | 天津仁智科技发展有限责任公司 | A kind of preparation method of the palladium on carbon powder as formaldehyde remover |
| CN108610792A (en) * | 2016-12-27 | 2018-10-02 | 天津众华鑫环保科技有限公司 | A kind of radiator formaldehyde eliminates the preparation method of coating |
| CN107413359A (en) * | 2017-08-24 | 2017-12-01 | 西安交通大学 | A kind of method on quick modified palladium catalyst surface |
| CN113373345A (en) * | 2021-06-07 | 2021-09-10 | 中氢新能(北京)新能源技术研究院有限公司 | Supported superfine PtCoP ternary alloy nanoparticle for electrocatalytic methanol oxidation and preparation method thereof |
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