CN103586484B - Pd-Ru alloy nano particle and its preparation and use - Google Patents

Pd-Ru alloy nano particle and its preparation and use Download PDF

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CN103586484B
CN103586484B CN201310604020.5A CN201310604020A CN103586484B CN 103586484 B CN103586484 B CN 103586484B CN 201310604020 A CN201310604020 A CN 201310604020A CN 103586484 B CN103586484 B CN 103586484B
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nano particle
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CN103586484A (en
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吴冬霜
曹荣
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Fujian Institute of Research on the Structure of Matter of CAS
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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
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    • Y02E60/50—Fuel cells

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Abstract

The invention discloses a kind of preparation method of binary metal alloy nanoparticle.The main component of the alloy nanoparticle is the palladium of polyvinylpyrrolidone protection and the uniform alloy of ruthenium; its preparation method is at a certain temperature; now ruthenium trichloride is added in the mixed solution of ethanedioic acid and polyvinylpyrrolidone; then the precursor salt of palladium is added; by the last handling process such as reduction-nucleation-curing and centrifugation, washing and drying; a kind of direct methanoic acid fuel cell anode catalyst of the present invention is ultimately formed, the mol ratio of two kinds of metals can be by the ratio of precursor salt come any regulation.The invention further relates to the application in direct methanoic acid fuel cell field is applied to as anode catalyst.

Description

Pd-Ru alloy nano particle and its preparation and use
Technical field
Polyvinylpyrrolidone be the present invention relates to the use of as protective agent and prepare palladium ruthenium conjunction of the particle diameter between 3~5 nanometers The method of gold nano grain, while being related to the application as direct methanoic acid fuel cell anode catalyst.By to two The optimal palladium ruthenium ratio in the effective screening alloy nanoparticle of regulation of metal precursor salt mol ratio is planted, is prepared with high Activity, the direct methanoic acid fuel cell anode catalyst of high stability, belong to fuel-cell catalyst preparation field.
Background technology
Compared with monometallic, alloy can greatly facilitate catalytic performance.For example, coming for anodic oxidation of methanol reaction Say, the catalytic effect of platinum-ruthenium alloys is much due to pure platinum.Palladium and platinum have similar lattice constant, and price is cheaper than platinum Many, earth's crust storage capacity is at least 50 times of platinum, is currently generally acknowledged preferable platinum substitute.And come for aminic acid fuel battery Say, the catalytic effect of palladium is better than platinum, because palladium does not produce carbon monoxide mainly by " direct way " come catalysis oxidation formic acid Etc. toxicity intermediate product.But Pd poor catalyst stabilities, easily oxidation, also one as direct methanoic acid fuel cell asks greatly Topic.Therefore the balance between catalytic activity and stability, performance and cost is still direct methanoic acid fuel cell Catalyst Design With the key point of preparation.Inspired by platinum-ruthenium alloys, Pd-Ru alloy is that can improve the activity of pure palladium chtalyst in theory, And improve its stability.But it is due to be limited to Hume-Rothery criterions, forms uniform between any two kinds of metals Alloy is very difficult.For bulk material, when temperature appreciate 500 DEG C when, only 0.5% ruthenium can penetrate into the lattice of palladium In.Therefore, synthesis uniformly constitutes adjustable Pd-Ru alloy and is still a challenge.
The synthesis for developing into alloy material of nanometer technology provides and carves machine.When particle drops to nanoscale, surface is certainly By be able to can greatly increase, so that the enthalpy of formation required during two kinds of metal formation alloys（Gibbs free energy）It can substantially reduce. Therefore in theory, when particle drops to nanoscale, two kinds of insoluble bulk materials can form uniform alloy.For example, reason Show by research when particle diameter is dropped to below 6 nanometers, gold and two kinds of insoluble block materials of platinum can form uniform alloy.Cause This, as long as reasonably controlling reaction condition, when size is dropped into certain nanoscale, just can form Pd-Ru alloy.
The content of the invention
It is an object of the invention to overcome the challenge that Hume-Rothery criterions are present, there is provided with polyvinylpyrrolidone Preparing particle diameter in 3~5 nanometers of Pd-Ru alloy particle as stabilizer is used for direct methanoic acid fuel cell anode catalyst, and leads to The ratio for controlling to adjust Pd and Ru in alloy to the mol ratio of metal precursor salt is crossed, to obtain the catalyst of most ratio of greater inequality.
The present invention is prepared for Pd-Ru alloy of the particle diameter at 3~5 nanometers using polyvinylpyrrolidone respectively as protective agent Nano particle is used for direct methanoic acid fuel cell anode catalyst.The present invention is by reduction temperature, the spy of presoma ratio etc. Rope, realizes the regulation of alloying component ratio and the control of particle size, so that it is adjustable to obtain ratio, the uniform palladium of particle diameter distribution Ruthenium alloy nano particle.Compared with commercially available palladium carbon, the palladium nanocatalyst prepared by the present invention is to the electrocatalytic oxidation table of formic acid Reveal excellent catalytic activity and stability.The preparation technology of the present invention is simple, easy to operate, can industrialization production.
The present invention provides a kind of preparation method of Pd-Ru alloy nano particle, comprises the following steps：
（1）Configuration concentration is the ethylene glycol solution 12.5ml of 8mg/ml polyvinylpyrrolidone；
（2）To step at 200 DEG C（1）The aqueous solution of a certain amount of ruthenium trichloride is added in middle configured solution, is obtained To mixture A；
（3）The potassium chloropalladate aqueous solution is added dropwise dropwise into mixture A, mixture B is obtained；
（4）Mixture B is cured at least 1 hour at 200 DEG C, stops reaction cooling；
（5）Step（4）The mixed liquor of the acetone centrifugation of about 5 times of volumes of obtained product, water and acetone（Volume ratio For 1：7）Cyclic washing sediment 3 times, the precipitation of final gained is the Pd-Ru alloy nano particle.
The present invention also provides the Pd-Ru alloy nano particle prepared according to preceding method, and its average grain diameter is 3-5nm. In the Pd-Ru alloy nano particle, palladium ruthenium mol ratio can be according to the addition flexible modulation of presoma.
The present invention is also provided, described Pd-Ru alloy nano particle answering as direct methanoic acid fuel cell anode catalyst With the mol ratio of palladium ruthenium is preferably 3 in this application:2.
The preparation method of binary metal alloy nanoparticle provided by the present invention has advantages below：The catalyst of preparation Uniform particle sizes, good dispersion is 3~5nm, and the spheroidal little particle surface of class, which has, is much coordinated unsaturated key, beneficial to formic acid Catalysis；In alloy there is this cooperative effect and electronic effect in Ru and Pd, so as to greatly increase Pd activity stability；With this one The catalyst that pot method method is prepared, catalytic activity height, service life length, renewable simple and easy to get with catalyst Strong advantage.
Brief description of the drawings
Catalyst Pd prepared by Fig. 160Ru40Light field large area transmission electron microscope photo；
The details in a play not acted out on stage, but told through dialogues high-resolution picture of any two adjacent nano particles in catalyst prepared by Fig. 2；
The angle of elevation annular dark of particle-scanning transmission charge pattern line sweeps curve in Fig. 3 Fig. 2（HAADF-STEM line scan）；
The X-ray diffractogram of the catalyst of different palladium ruthenium ratios prepared by Fig. 4（XRD）；
Catalyst and commercially available palladium carbon (Pd/C) catalyst prepared by Fig. 5 is right in 0.1mol/L perchloric acid solutions 0.25mol/L formic acid electrocatalytic oxidation cyclic voltammograms；
The time current curve of Fig. 6 catalyst.
Fig. 1-3 device therefors are JEOL-2010, the use of voltage are 200 kilovolts；Fig. 4 equipment Rigaku D/max-2500X- ray generator；Fig. 5 and 6 equipment are Epsilon EC electrochemical work station（BASi, the U.S.）.
Embodiment
Make further details of second speed to the present invention with reference to embodiment and accompanying drawing to return, but be not intended to limit the present invention.
Case study on implementation 1, prepares Pd90Ru10Alloy nanoparticle, its average grain diameter is 3.1nm.
(1) configuration concentration is the ethylene glycol solution 12.5ml of 8mg/ml polyvinylpyrrolidone；
(2) at 200 DEG C, to step（1）The ruthenium trichloride that 10 μ l concentration are 0.3mol/L is added in obtained mixed liquor The aqueous solution, obtains mixture A；
(3) the potassium chloropalladate aqueous solution that 3ml concentration is 8.3mmol/L is added dropwise dropwise into mixture A, mixture B is obtained；
(4) mixture B is cured at least 1 hour at 200 DEG C, stops reaction cooling；
(5) by step（4）Obtained product is separated with 65ml acetone（7900 turns/8 minutes）, 5ml water is plus 35ml Acetone cyclic washing at least 3 times（14000 turns/10 minutes）, gained precipitation is direct methanoic acid fuel cell sun of the present invention Electrode catalyst, its Pd and Ru atomic ratio are 9：1, it is designated as Pd90Ru10。
Case study on implementation 2, prepares Pd60Ru40Alloy nanoparticle, its average grain diameter is 3.8nm.
(1) configuration concentration is the ethylene glycol solution 12.5ml of 8mg/ml polyvinylpyrrolidone；
(2) at 200 DEG C, to step（1）The ruthenium trichloride that 100 μ l concentration are 0.3mol/L is added in obtained mixed liquor The aqueous solution, obtains mixture A；
(3) the potassium chloropalladate aqueous solution that 3ml concentration is 8.3mmol/L is added dropwise dropwise into mixture A, mixture B is obtained；
(4) mixture B is cured at least 1 hour at 200 DEG C, stops reaction cooling；
(5) by step（4）Obtained product is separated with 65ml acetone（7900 turns/8 minutes）, 5mL water is plus 35ml Acetone cyclic washing at least 3 times（14000 turns/10 minutes）, gained precipitation is direct methanoic acid fuel cell sun of the present invention Electrode catalyst, its Pd and Ru atomic ratio are 3：2, it is designated as Pd60Ru40。
Case study on implementation 3, prepares Pd20Ru80Alloy nanoparticle, its average grain diameter is 4.2nm.
(1) configuration concentration is the ethylene glycol solution 12.5ml of 8mg/ml polyvinylpyrrolidone；
(2) at 200 DEG C, to step（1）The ruthenium trichloride that 240 μ l concentration are 0.3mol/L is added in obtained mixed liquor The aqueous solution, obtains mixture A；
(3) the potassium chloropalladate aqueous solution that 1.5ml concentration is 8.3mmol/L is added dropwise dropwise into mixture A, mixture is obtained B；
(4) mixture B is cured at least 1 hour at 200 DEG C, stops reaction cooling；
(5) by step（4）Obtained product is separated with 65ml acetone（7900 turns/8 minutes）, 3mL water is plus 30ml Acetone cyclic washing at least 3 times（14000 turns/10 minutes）, gained precipitation is direct methanoic acid fuel cell sun of the present invention Electrode catalyst, its Pd and Ru atomic ratio are 1：4, it is designated as Pd20Ru80。
Case study on implementation 4, with Pd60Ru40Exemplified by, prepare the glass carbon electricity of direct methanoic acid fuel cell surface catalysis oxidant layer modification Pole.
(1) by the Pd prepared by case study on implementation 260Ru40Alloy nanoparticle ultrasonic disperse leads in 8ml ethanol solution Cross atomic emission spectrum（ICP）Determine Pd and Ru concentration and quality.
(2) by step（1）The activated carbon mixing of the scattered nano particle of middle ethanol and certain mass, and add the different of 2ml Then propyl alcohol, ultrasound 4 hours stirs 48 hours at room temperature.According to step（1）The ICP results surveyed, the activated carbon added Quality is about 9 times of Pd mass in alloy nanoparticle.
(3) to step（2）In prepared mixture add 30ml acetone, centrifuge out precipitation（14000 turns/8 points Clock）And then with isopropanol and the mixed liquor of acetone（Volume ratio is 1：7）Wash and centrifuge（14000 turns/8 minutes）, by what is obtained Precipitation is dried in vacuum overnight, and obtains activated carbon supported palladium nanocatalyst.
(4) step is tested out by ICP（3）Pd mass fraction in the activated carbon supported palladium nanocatalyst of middle gained, Then it is dispersed in ethanol, the content for making palladium is 1mg/ml.
(5) 3mm glass-carbon electrode is polished with 1.0,0.3,0.05 μm of alumina powder successively, and be cleaned by ultrasonic clean In smooth minute surface, dried for standby.
(6) the step of taking 3 μ l（4）The glass-carbon electrode in a diameter of 3mm is added dropwise in the alcohol dispersion liquid of middle loaded catalyst Surface, is spontaneously dried at room temperature.
(7) to step（6）4 μ l Nafion are added dropwise in the electrode surface of middle preparation（PEM, mass fraction is 5% Ethanol solution）, the glass-carbon electrode of surface catalysis oxidant layer modification is produced after spontaneously drying at room temperature.
Case study on implementation 5, with Pd60Ru40Exemplified by the glass-carbon electrode of modification, the measure of the cyclic voltammetry curve of catalyst is carried out.
（1）The chemical property of catalyst is determined using three-electrode system.With the above-mentioned surface catalysis oxidant layer prepared Glass-carbon electrode as working electrode, platinum filament is that Ag/AgCl is reference electrode to electrode.
（2）The aqueous solution of 0.1mol/L perchloric acid leads to nitrogen to remove the oxygen in solution in advance.
（3）The glass-carbon electrode of gained in case study on implementation 4 is activated, activation method is in step（2）The high chlorine of gained Cyclic voltammetry scan is carried out in aqueous acid and knows that the curve of gained is stable, the voltage range of scanning is elected -0.3~1.0V as, swept Speed is retouched for 0.2V/s, temperature is room temperature.
（4）To step（2）A certain amount of formic acid is added in the aqueous solution of the 0.1mol/L perchloric acid of gained so that formic acid Ultimate density is measure cyclic voltammetry curve and timing Ampere currents curve under 0.25mol/L, room temperature condition.Wherein cyclic voltammetric The voltage range of curved scanning elects -0.3~0.9V as, and sweep speed is 0.05V/s.The voltage of timing Ampere currents curve is fixed In 0.2V, the testing time is 1500s.
Fig. 1 is the transmission electron microscope photo for the catalyst that case study on implementation 2 is provided, as can see from Figure 1 synthesized catalysis Agent be uniformly dispersed, narrow particle size distribution, average grain diameter be 3.8nm class ball little particle.Fig. 2 is two phases of any selection The details in a play not acted out on stage, but told through dialogues high-resolution picture of adjacent nano particle, Fig. 3 is that corresponding angle of elevation annular dark-scanning transmission charge pattern line sweeps song Line, it can be seen that existing Ru has Pd signal, and Pd and Ru variation tendency basic one again on each information gathering point Cause（With liter with drop）, it is uniform alloy to illustrate the particle.Fig. 4 provides the XRD curves of the PdRu alloys of different component, can be with it In endways solid line represent Pd（111）Face, dotted line represents Ru（101）Face, it can be seen that all PdRu alloys are all two There is a strong diffraction maximum between bar vertical line, and peak position is moved with Ru increase to high angle, this is from another angle The PdRu alloys for illustrating generation are pure phase, do not contain the impurity such as Pd or Ru simple substance.
Fig. 5 provides different-alloy and commercially available Pd/C（Aldrich）Catalyst is swept to the forward direction of the catalytic curve of formic acid The block diagram for the peak value retouched, it can be seen that Pd60Ru40There is highest Catalyzed by Formic Acid electric current, current density when 0.23 volt It is 0.61 milliampere of every micro- palladium, is 4.1 times of commercial catalyst.When Ru ratio is below or above 40%, catalytic activity all can Reduction.The timing Ampere currents curve that Fig. 6 is provided is it can also be seen that the stability of PdRu alloys is better than pure Pd catalyst and city Sell Pd/C catalyst.After 1500 seconds, remaining electric current is much larger than commercially available Pd/C catalyst.
Above said content is only the basic explanation under present inventive concept, and according to appointing that technical scheme is done What equivalent transformation, all should belong to protection scope of the present invention.

Claims (3)

1. the preparation method of Pd-Ru alloy nano particle, comprises the following steps：
(1) configuration concentration is the ethylene glycol solution 12.5ml of 8mg/ml polyvinylpyrrolidone；
(2) aqueous solution of a certain amount of ruthenium trichloride is added in the solution configured at 200 DEG C into step (1), is mixed Compound B；
(3) the potassium chloropalladate aqueous solution is added dropwise dropwise into mixture B, mixture C is obtained；
(4) mixture C cures at least 1 hour, Temperature fall at a temperature of 200 DEG C；
(5) product that step (4) the is obtained acetone centrifugation of about 5 times of volumes, uses volume ratio for 1：7 water and acetone Mixed liquor cyclic washing sediment 3 times, the precipitation of final gained is the Pd-Ru alloy nano particle；
Wherein, Pd and Ru atomic ratio is 9:1,3:1,3:2 or 2:3.
2. the Pd-Ru alloy nano particle prepared using claim 1 methods described, its average grain diameter is 3-5nm.
3. Pd-Ru alloy nano particle described in claim 2 is used as the application of direct methanoic acid fuel cell anode catalyst.
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