CN102078811B - Method for preparing carbon loading Pd nanometer particle catalyst by using homogeneous precipitation-reduction in situ method - Google Patents
Method for preparing carbon loading Pd nanometer particle catalyst by using homogeneous precipitation-reduction in situ method Download PDFInfo
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- CN102078811B CN102078811B CN2010106050538A CN201010605053A CN102078811B CN 102078811 B CN102078811 B CN 102078811B CN 2010106050538 A CN2010106050538 A CN 2010106050538A CN 201010605053 A CN201010605053 A CN 201010605053A CN 102078811 B CN102078811 B CN 102078811B
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- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses a method for preparing a Pd nanometer particle catalyst by using a homogeneous precipitation-reduction in situ method, which comprises the following steps of: adding a soluble PdII salt solution into a certain quantity of carbon carrier suspending solution; regulating pH of a mixture solution to be between 5.6 and 7.4; heating the solution at 30-100 DEG C; heating and hydrolyzing the soluble PdII salt solution to obtain a component A, i.e. carbon loading PdO.H2O nanometer particles; adding over-dose reducing agents into the component A and fully stirring so that the carbon loading PdO.H2O nanometer particles are fully reacted with the reducing agents; carrying out the reduction in-situ to obtain a component B; washing the component B; and drying the component B under the protection of vacuum or inert gases to obtain the carbon loading Pd nanometer particle (Pd/c) catalyst. The catalyst obviously improves the electro-catalysis performance of formic acid and shows excellent electro-catalysis activity and stability. The preparation method of the invention is simple and economic, and is suitable for industrial large-scale production.
Description
Technical field
The present invention relates to a kind of preparation method of direct methanoic acid fuel cell catalyst, particularly relate to a kind of precipitation from homogeneous solution-in-situ reducing principle of utilizing and pass through Pd
II→ PdOH
2O → Pd
0Reaction path prepares the method that charcoal carries the Pd nano-particle catalyst.
Background technology
Fuel cell becomes following best " clean energy resource " owing to having the advantages such as energy conversion efficiency is high, environmental pollution is little.Therefore, fuel cell is the focus of paying close attention in the new forms of energy development strategy always.In recent years, because direct methanoic acid fuel cell can as electrical source of power and the Portable movable power supply of electric vehicle, receive increasing concern.Formic acid is in liquid state at normal temperatures, and freezing point is low and nontoxic, and is nonflammable, is applicable to low-temperature working, and comparatively safe.Direct methanoic acid fuel cell has many having a few than DMFC.Such as, formic acid is nontoxic, and it is permitted as food additives by food and drug administration; The electrochemistry oxidation performance of formic acid is more much better than methyl alcohol; Formic acid to the permeability of Nafion film much smaller than methyl alcohol; Nonflammable in addition simultaneously, but the advantages such as high concentration use more and more receive numerous researchers' concern.
Studies show that, in direct methanoic acid fuel cell, the electrochemical reaction of formic acid on Pd mainly is direct oxidation pathway, and its product is CO
2And water, and poison species CO in the middle of not having, so palladium and palladium-based catalyst are the first-selected catalyst of direct methanoic acid fuel cell.In general, the antianode catalyst has several basic requirements, namely high electro catalytic activity, stability and electron conduction will be arranged.At present, the direct methanoic acid fuel cell anode catalyst is generally palladium and palladium based composite catalyst, it is active that Pd metal pair formic acid has unique catalytic oxidation, but because the Metal Palladium price is more expensive, resource-constrained, must take effective measures the carrying capacity that reduces palladium, reduce as far as possible the Pd metal consumption, improve the decentralization of Pd.Polymolecularity, uniformity are necessary conditions of preparation high activated catalyst.And method for preparing catalyst is to the catalyst decentralization, particle size and distribution, and active surface area, the aspects such as the utilization rate of catalyst all have a great impact, thereby have influence on electro catalytic activity and the stability of catalyst.Therefore, exploring the method that can be used for the preparation of industrialization high performance catalyst is a problem that merits attention.
At present, the preparation research of charcoal supported noble metal catalyst is more mainly is divided into following several method: dipping-liquid phase reduction, micro emulsion method, colloid method, electro-deposition, the hot method of hydrothermal/solvent, glycol method, complexing-reducing process etc.For large-scale industrial production, liquid phase reduction is because simple to operate, and cost is low, the most easily realizes.Yet " local overrich " phenomenon easily causes the reunion of Pd nano particle in the reducing agent adding procedure, causes the catalyst pellets molecular dispersivity relatively poor.For PdCl under the strong acidic condition
2Solution, [PdCl
4]
2Mainly to have species.Raise [PdCl with pH
4]
2In Cl
Part can be progressively by H
2The O molecule replaces, and proton (equation 1-8) is lost in the experience hydrolysis.
These hydrolysates finally can transform and generate PdOH
2The O nano particle.On the principle, PdOH
2The size of O nano particle and dispersed size and the dispersiveness that determines end product Pd nano particle.Like this, by under suitable pH, make solubility Pd
IISalting liquid is by being heated, and the charcoal that utilizes the precipitation from homogeneous solution principle can prepare small size and polymolecularity carries PdOH
2The O nano particle.After the reduction, the charcoal of small size and polymolecularity carries Pd nano particle (Pd/C) catalyst and can be synthesized.
Summary of the invention
The Pd/C catalyst that the purpose of this invention is to provide a kind of small particle diameter, high performance direct methanoic acid fuel cell---charcoal carries the preparation method of ultra-fine Pd catalyst, and this catalyst can present very high catalytic activity and stability to the electrochemical oxidation of formic acid.
The technical scheme of finishing the foregoing invention task is:
A kind of method of preparing carbon loading Pd nanometer particle catalyst by using homogeneous precipitation-reduction in situ is characterized in that: add solubility Pd in water
IISalting liquid and charcoal carrier, mixture solution pH value is adjusted to 5.6 ~ 7.4, and mechanical agitation or sonic oscillation heat to get under 30 ~ 100 ℃ that component A---charcoal carries PdOH
2The suspension of O nano particle;
In component A, slowly add equivalent or excessive reductant, fully stir, make charcoal wherein carry PdOH
2O nano particle and reducing agent fully react, thereby the metal Pd nano particle original position that restores is fixed on the charcoal carrier, get B component;
Washing component B, dry under vacuum or the inert gas shielding, make described charcoal and carry the Pd nano-particle catalyst.
More particularly, precipitation from homogeneous solution-local reduction way of the present invention prepares the method for Pd/C catalyst, may further comprise the steps:
1) catalyst precursor precipitation from homogeneous solution: in water, add a certain amount of charcoal carrier and a certain proportion of solubility Pd
IISalting liquid, metal Pd mass percent in the catalyst integral body of load is 1～80%, said mixture is regulated pH to 5.6 ~ 7.4, and mechanical agitation or sonic oscillation mixed in 0.5～48 hour, heated 2～48 hours to such an extent that component A---charcoal carries PdOH at 30 ~ 100 ℃
2The suspension of O nano particle;
2) precipitation in-situ reducing: the component A that step 1) obtains slowly adds equivalent or excessive reductant under 0 ~ 80 ℃ of condition, mechanical agitation or sonic oscillation 0.5 ~ 8 hour make the PdOH among the component A
2Fully reaction occurs in O nano particle and reducing agent, and the metal Pd nano particle original position that restores is fixed on the charcoal carrier, gets B component;
3) washing component B that post processing: with step 2) obtains repeatedly, and with liquor argenti nitratis ophthalmicus check, until in the eluate without chlorion, then 20～50 ℃ of dryings under vacuum or inert gas atmosphere namely make the carrier loaded Pd/C catalyst of charcoal.
Described solubility Pd
IISalting liquid is PdCl
2, K
2PdCl
4, Na
2PdCl
4, Pd (NO
3)
2Or Pd (C
2H
3O
2)
2In one or more.
Described charcoal carrier is one or more in active carbon, CNT, carbon molecular sieve, carbon fiber or the Graphene.
The mol ratio of described Pd and described reducing agent is 1: 1 ~ 30.
Described reducing agent is hydrogen, NaBH
4, sodium hypophosphite or sodium phosphite.
Described inert gas atmosphere is Ar and N
2Deng.
The particle size of the Pd/C catalyst P d metal that precipitation from homogeneous solution-local reduction way of the present invention makes is 2.0～4.0 nm.
The inventive method utilizes the precipitation from homogeneous solution principle to pass through Pd
II→ PdOH
2O → Pd
0The Pd/C catalyst that reaction path prepares, wherein Pd particle size is 2.0～4.0 nm, average grain diameter is 3.0 nm approximately.The Pd/C catalyst that particle size is suitable compares NaBH
4The Pd/C of conventional liquid phase reduction preparation shows very excellent electro catalytic activity and stability.
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not limited with the specific embodiment, but is limited by claim.
Description of drawings
Fig. 1: the X-ray diffractogram of 20% Pd/C catalyst (XRD);
Fig. 2: the TEM photo of 20% Pd/C catalyst, Pd metallic average grain diameter 3.0 nm;
Fig. 3: conventional NaBH
4(curve a) and utilize Pd/C catalyst (curve b) that precipitation from homogeneous solution-local reduction way makes at 0.5 mol/L HCOOH+0.5mol/L H for the Pd/C catalyst that reducing agent makes
2SO
4Cyclic voltammogram in the solution, sweep speed: 50 mV/s, temperature: 30 ℃.
The specific embodiment
Example one:
The method of preparing carbon loading Pd nanometer particle catalyst by using homogeneous precipitation-reduction in situ may further comprise the steps:
1, takes by weighing Vulcan XC-72R activated carbon powder 60 mg of Cabot company, add 3.13 ml, 0.045 mol/L PdCl
2Solution, regulator solution pH value to 5.6 ~ 7.4 subsequently, high-speed stirred (or sonic oscillation) 0.5 ~ 48 hour was so that mix, 30 ~ 100 ℃ of heating water baths 2 hours.
2, (25 ℃) under the room temperature slowly add excessive reductant solution (NaBH
4), mechanical agitation 1 hour makes slaine and reducing agent complete reaction.
3, after washing repeatedly, and with liquor argenti nitratis ophthalmicus check, until in the eluate without chlorion.At N
2The lower 50 ℃ of dryings of condition namely make the metal carrying capacity and are 20% Pd/C catalyst, and wherein catalyst particle size is about 2.0 ~ 4.0 nm.
Example two:
The method of preparing carbon loading Pd nanometer particle catalyst by using homogeneous precipitation-reduction in situ may further comprise the steps:
1, taking by weighing the self-control caliber is 10-20nm CNT (CNTs) 60 mg, adds 3.13 ml, 0.045 mol/L PdCl
2, regulator solution pH value to 5 ~ 7 subsequently, high-speed stirred (or sonic oscillation) 0.5 ~ 48 hour is so that mix.
2, (25 ℃) under the room temperature slowly add excessive reductant solution (NaBH
4), mechanical agitation 1 hour made slaine and reducing agent complete reaction, 30 ~ 100 ℃ of heating water baths 2 hours.
3, after washing repeatedly, and with liquor argenti nitratis ophthalmicus check, until in the eluate without chlorion.At N
2The lower 50 ℃ of dryings of gas condition namely make the metal carrying capacity and are 20% Pd/CNTs catalyst, and wherein catalyst particle size is about 1.5 ~ 4.0nm.
Example three
The method of preparing carbon loading Pd nanometer particle catalyst by using homogeneous precipitation-reduction in situ may further comprise the steps:
1, takes by weighing carbon molecular sieve 60 mg, add 3.13 ml, 0.045 mol/L PdCl
2Solution, regulator solution pH value to 5 ~ 7 subsequently, high-speed stirred (or sonic oscillation) 0.5 ~ 48 hour was so that mix, 30 ~ 100 ℃ of heating water baths 2 hours.
2, (25 ℃) under the room temperature slowly add excessive reductant solution (NaBH
4), mechanical agitation 1 hour makes slaine and reducing agent complete reaction.
3, after washing repeatedly, and with liquor argenti nitratis ophthalmicus check, until in the eluate without chlorion.At N
2The lower 50 ℃ of dryings of gas condition namely make the metal carrying capacity and are the Pd nano-particle catalyst of 20% carbon molecular sieve load, and wherein catalyst particle size is about 2.0 ~ 4.0 nm.
Example four
The method of preparing carbon loading Pd nanometer particle catalyst by using homogeneous precipitation-reduction in situ may further comprise the steps:
1, takes by weighing Graphene 60 mg, add 3.13ml 0.045 mol/L PdCl
2Solution,, regulator solution pH value to 5 ~ 7 subsequently, high-speed stirred (or sonic oscillation) 0.5 ~ 48 hour was so that mix, 30 ~ 100 ℃ of heating water baths 2 hours.
2, (25 ℃) under the room temperature slowly add excessive reductant solution (NaBH
4), mechanical agitation 1 hour makes slaine and reducing agent complete reaction.
3, after washing repeatedly, and with liquor argenti nitratis ophthalmicus check, until in the eluate without chlorion.At N
2The lower 50 ℃ of dryings of gas condition namely make the metal carrying capacity and are 20% graphene-supported Pd catalyst, and wherein catalyst particle size is about 2.0 ~ 4.0 nm.
Example five
The method of preparing carbon loading Pd nanometer particle catalyst by using homogeneous precipitation-reduction in situ may further comprise the steps:
1, takes by weighing carbon fiber 60 mg, add 3.13 ml, 0.045 mol/L K
2PdCl
4Solution,, regulator solution pH value to 5 ~ 7 subsequently, high-speed stirred (or sonic oscillation) 0.5 ~ 48 hour was so that mix, 30 ~ 100 ℃ of heating water baths 2 hours.
2, (25 ℃) under the room temperature slowly add excessive reductant solution (NaBH
4), mechanical agitation 1 hour makes slaine and reducing agent complete reaction.
3, after washing repeatedly, and with liquor argenti nitratis ophthalmicus check, until in the eluate without chlorion.At N
2The lower 50 ℃ of dryings of gas condition namely make the metal carrying capacity and are 20% graphene-supported Pd catalyst, and wherein catalyst particle size is about 2.0 ~ 4.0 nm.
Example six:
The method of preparing carbon loading Pd nanometer particle catalyst by using homogeneous precipitation-reduction in situ may further comprise the steps:
1, takes by weighing Vulcan XC-72R activated carbon powder 60 mg of Cabot company, add 3.13ml 0.045 mol/L K
2PdCl
4Solution, regulator solution pH value to 5.6 ~ 7.4 subsequently, high-speed stirred (or sonic oscillation) 0.5 ~ 48 hour was so that mix, 30 ~ 100 ℃ of heating water baths 2 hours.
2, (25 ℃) under the room temperature slowly add excessive reductant solution (NaBH
4), mechanical agitation 1 hour makes slaine and reducing agent complete reaction.
3, after washing repeatedly, and with liquor argenti nitratis ophthalmicus check, until in the eluate without chlorion.At N
2The lower 50 ℃ of dryings of gas condition namely make the metal carrying capacity and are 20% Pd/C catalyst, and wherein catalyst particle size is about 2.0 ~ 4.0 nm.
Example seven:
The method of preparing carbon loading Pd nanometer particle catalyst by using homogeneous precipitation-reduction in situ may further comprise the steps:
1, takes by weighing Vulcan XC-72R activated carbon powder 60 mg of Cabot company, add 3.13 ml, 0.045 mol/L Na2PdCl4 solution, regulator solution pH value to 5.6 ~ 7.4 subsequently, high-speed stirred (or sonic oscillation) 0.5 ~ 48 hour was so that mix, 30 ~ 100 ℃ of heating water baths 2 hours.
2, (25 ℃) under the room temperature slowly add excessive reductant solution (NaBH4), and mechanical agitation 1 hour makes slaine and reducing agent complete reaction.
3, after washing repeatedly, and with liquor argenti nitratis ophthalmicus check, until in the eluate without chlorion.50 ℃ of dryings under N2 gas condition namely make the metal carrying capacity and are 20% Pd/C catalyst, and wherein catalyst particle size is about 2.0 ~ 4.0 nm.
Fig. 1 is that the metal carrying capacity is the XRD collection of illustrative plates of 20% Pd/C catalyst.Can primary Calculation obtain the average grain diameter of the metallic in the Pd catalyst greatly about 3 nm according to the XRD collection of illustrative plates.Curve a is the Pd/C catalyst that conventional liquid phase reduction makes among the figure, and curve b is the Pd/C catalyst of precipitation from homogeneous solution of the present invention-local reduction way preparation.
Fig. 2 is the TEM photo of 20% Pd/ catalyst.Photo clearly demonstrates the charcoal that makes by deposition sedimentation in-situ reducing method and carries the Pd catalyst, and the average grain diameter of metallic is greatly about 3 nm, and metallic has good homogeneity and decentralization.
Fig. 3 is conventional NaBH
4(curve a) and utilize Pd/C catalyst (curve b) that precipitation from homogeneous solution-local reduction way makes at 0.5 mol/L HCOOH+0.5mol/L H for the Pd/C catalyst that reducing agent makes
2SO
4Cyclic voltammogram in the solution.The spike potential of the Pd/C catalyst that makes with precipitation from homogeneous solution-local reduction way is than conventional NaBH
4The Pd/C catalyst that reducing process makes is negative to have moved 50 mV, and peak current is also obviously many greatly, and the Pd/C catalyst is obviously higher to the electro catalytic activity of formic acid.The Oxidation of Formic Acid peak of just sweeping on the direction at the cyclic voltammetry curve current potential all appears at about 0.20 V, but peak current density is different.Pd/C catalyst and NaBH that formic acid makes at precipitation from homogeneous solution-local reduction way
4The peak current density of oxidation is respectively 956.6 and 321.9A/g on the similar Pd/C catalyst of conventional liquid-phase reduction.Compare NaBH
4The similar Pd/C catalyst of conventional liquid-phase reduction, the Pd/C catalyst that the present invention makes has improved 3 times nearly to the electrocatalytic oxidation property of formic acid.
Claims (8)
1. the method for a preparing carbon loading Pd nanometer particle catalyst by using homogeneous precipitation-reduction in situ is characterized in that:
In water, add solubility Pd
IISalting liquid and charcoal carrier, mixture solution pH value is adjusted to 5.6 ~ 7.4, and mechanical agitation or sonic oscillation heat to get under 30 ~ 100 ℃ that component A---charcoal carries PdOH
2The suspension of O nano particle;
In component A, slowly add equivalent or excessive reductant, fully stir, make charcoal wherein carry PdOH
2O nano particle and reducing agent fully react, thereby the metal Pd nano particle original position that restores is fixed on the charcoal carrier, get B component;
Washing component B, dry under vacuum or the inert gas shielding, make described charcoal and carry the Pd nano-particle catalyst.
2. the method for preparing carbon loading Pd nanometer particle catalyst by using homogeneous precipitation-reduction in situ according to claim 1 is characterized in that described method may further comprise the steps:
1) catalyst precursor precipitation from homogeneous solution: in water, add a certain amount of charcoal carrier and a certain proportion of solubility Pd
IISalting liquid, metal Pd mass percent in the catalyst integral body of load is 1～80%, said mixture is regulated pH to 5.6 ~ 7.4, and mechanical agitation or sonic oscillation mixed in 0.5～48 hour, heated 2～48 hours to such an extent that component A---charcoal carries PdOH at 30 ~ 100 ℃
2The suspension of O nano particle;
2) precipitation in-situ reducing: the component A that step 1) obtains slowly adds equivalent or excessive reductant under 0 ~ 80 ℃ of condition, mechanical agitation or sonic oscillation 0.5 ~ 8 hour make the PdOH among the component A
2Fully reaction occurs in O nano particle and reducing agent, and the metal Pd nano particle original position that restores is fixed on the charcoal carrier, gets B component;
3) washing component B that post processing: with step 2) obtains repeatedly, and with liquor argenti nitratis ophthalmicus check, until in the eluate without chlorion, then 20～50 ℃ of dryings under vacuum or inert gas atmosphere namely make the carrier loaded Pd/C catalyst of charcoal.
3. the method for preparing carbon loading Pd nanometer particle catalyst by using homogeneous precipitation-reduction in situ according to claim 1 and 2 is characterized in that: described solubility Pd
IISalting liquid is PdCl
2, K
2PdCl
4, Na
2PdCl
4, Pd (NO
3)
2Or Pd (C
2H
3O
2)
2In one or more.
4. the method for preparing carbon loading Pd nanometer particle catalyst by using homogeneous precipitation-reduction in situ according to claim 1 and 2, it is characterized in that: described charcoal carrier is one or more in active carbon, CNT, carbon molecular sieve, carbon fiber or the Graphene.
5. the method for preparing carbon loading Pd nanometer particle catalyst by using homogeneous precipitation-reduction in situ according to claim 1 and 2, it is characterized in that: the mol ratio of described Pd and described reducing agent is 1: 1 ~ 30.
6. the method for preparing carbon loading Pd nanometer particle catalyst by using homogeneous precipitation-reduction in situ according to claim 1 and 2, it is characterized in that: described reducing agent is hydrogen, NaBH
4, sodium hypophosphite or sodium phosphite.
7. the method for preparing carbon loading Pd nanometer particle catalyst by using homogeneous precipitation-reduction in situ according to claim 1 and 2, it is characterized in that: described inert gas atmosphere is Ar or N
2
8. the method for preparing carbon loading Pd nanometer particle catalyst by using homogeneous precipitation-reduction in situ according to claim 1 and 2, it is characterized in that: the particle size of described Pd/C catalyst P d metal is 2.0～4.0 nm.
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| CN102658126A (en) * | 2012-05-21 | 2012-09-12 | 上海电力学院 | Method for preparing Pd/C nano catalyst |
| CN103495430A (en) * | 2013-10-16 | 2014-01-08 | 西华师范大学 | Phosphorus-doped graphene oxygen reduction electro-catalyst and preparation method and application thereof |
| CN103934470B (en) * | 2014-04-04 | 2016-01-20 | 中南大学 | A kind of preparation method of Marks decahedron Pd nano particle |
| CN104368335B (en) * | 2014-10-15 | 2016-08-17 | 深圳市艾迪盈创科技有限公司 | A kind of preparation method and applications of purifying formaldehyde noble metal monolithic catalyst |
| CN104409741A (en) * | 2014-11-06 | 2015-03-11 | 中南大学 | Carbon-supported palladium oxide oxidation-reduction electro-catalyst and preparation method thereof |
| CN104607186B (en) * | 2015-02-05 | 2017-02-22 | 广西师范大学 | Multiwalled carbon nanotube-loaded PdSn catalyst based on deep eutectic solvent, and preparation method and application of catalyst |
| CN104815649B (en) * | 2015-04-14 | 2017-05-17 | 陕西师范大学 | Method for preparing high-activity Pd nano particle-supported carbon catalyst by diglycol reduction process |
| CN105355935B (en) * | 2015-11-11 | 2018-04-10 | 大连理工大学 | A kind of preparation method and application of noble metal electrocatalyst |
| CN105797720A (en) * | 2016-05-16 | 2016-07-27 | 北京化工大学 | Superfine supported noble metal catalyst prepared through in-situ reduction deposition method and preparing method thereof |
| CN107742733A (en) * | 2017-10-27 | 2018-02-27 | 新疆大学 | A kind of preparation method of the fiber-loaded palladium catalyst of coal-based carbon |
| CN107876047B (en) * | 2017-11-19 | 2021-01-05 | 西安凯立新材料股份有限公司 | Preparation method of Pd/C catalyst for alpha, beta-unsaturated aldehyde/ketone hydrogenation |
| CN109167069B (en) * | 2018-07-17 | 2021-03-23 | 常州大学 | Preparation method of high-activity electrode with metal loaded on binary carrier containing molecular sieve |
| CN114188553A (en) * | 2021-12-01 | 2022-03-15 | 武汉理工大学 | Pd/Co-C catalyst, and preparation method and application thereof |
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| 陈滢等.用改进液相还原法制备炭载Pd催化剂.《应用化学》.2009,第26卷(第8期), * |
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Granted publication date: 20130213 Termination date: 20161226 |
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| CF01 | Termination of patent right due to non-payment of annual fee |