CN104975346A - Pd-Pt alloy nanocrystalline, and preparation method and applications thereof - Google Patents
Pd-Pt alloy nanocrystalline, and preparation method and applications thereof Download PDFInfo
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- CN104975346A CN104975346A CN201510376890.0A CN201510376890A CN104975346A CN 104975346 A CN104975346 A CN 104975346A CN 201510376890 A CN201510376890 A CN 201510376890A CN 104975346 A CN104975346 A CN 104975346A
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Abstract
The invention belongs to the field of nano material, and specifically discloses a Pd-Pt alloy nanocrystalline, and a preparation method and applications thereof. The Pd-Pt alloy nanocrystalline is a concave polyhedron, and the crystalline phase of the Pd-Pt alloy nanocrystalline is a face-centered cubic phase. The Pd-Pt alloy nanocrystalline possesses excellent ORR and OER performance, and is capable of realizing high efficiency catalysis of ORR and OER in fuel cells. According to the preparation method, one-pot procedure is adopted, the Pd-Pt alloy nanocrystalline is obtained via a program controlling temperature mode, the preparation method is simple, reaction temperature is low, time is short, and the preparation method is suitable for industrialized batch production.
Description
Technical field
The invention discloses a kind of Pd-Pt alloy nanometer crystals and its preparation method and application, belong to nm regime.
Background technology
Along with world energy sources needs and the increase day by day of environmental problem, searching clean energy is extremely urgent.In recent years, the exploitation of fuel cell, have widened the research range of energy field further.Metallic nano crystal, due to the geometry of its uniqueness and its distinctive optics, electricity, catalysis and mechanical characteristic, attracts wide attention at a lot of key areas.In metal nano race, noble metal nanocrystalline (as Au, Ag, Pd and Pt etc.) and alloy nanometer crystals (FePt, etc. PdPt) be widely used in a lot of fields, particularly have that the bimetallic alloy of special appearance is nanocrystalline potential application in fuel cell field.Such as, Sun seminar is controlledly synthesis Fe-Pt alloy nanometer crystals in oleyl amine system, shows superior ORR in an acidic solution active.The branched Pd-Pt of controlledly synthesis is nanocrystalline in aqueous in Xia seminar, and electro-chemical test shows, branched Pd-Pt is nanocrystalline has the avtive spot more compared with large specific surface sum, thus improves catalytic activity and the stability of catalyzer.
But still there is following problem: Pt nanocrystalline catalyst is catalytic oxidation-reduction reaction (ORR) the most effective catalyzer, and for oxygen evolution reaction (OER), the nanocrystalline catalytic activity of Pt is poor, thus make it widely use to be restricted.It should be noted that the alloy nanometer crystals synthesis condition with highly active special construction is general comparatively numerous and diverse, and seldom researcher pays close attention to its bi-functional simultaneously.
Therefore, research and develop the focus that efficient difunctional Pt nanocrystalline catalyst is research at present, in the evolution of renewable energy technologies, seek the alloy nanometer crystals of efficient special construction, particularly can be used for the significant and huge challenge of the bifunctional electrocatalyst of ORR and OER.
Summary of the invention
The present invention is intended to a kind of novel, efficient dual-function catalyst of exploitation.
In order to realize this purpose, we disclose a kind of Pd-Pt alloy nanometer crystals, described Pd-Pt alloy nanometer crystals is concave polyhedron, and its crystalline phase is face-centered cubic phase.
Pd-Pt alloy nanometer crystals disclosed in the present invention is prepared as follows to obtain: by Pd (NO
3)
2 . 2H
2o, H
2ptCl
6 . 6H
2o, polyvinylpyrrolidone (PVP), cetyl trimethylammonium bromide (CTAB) joins in ethylene glycol solution, progressively be warming up to 110-230 ° of C, and the product be obtained by reacting at this temperature containing Pd-Pt alloy nanometer crystals, obtain Pd-Pt alloy nanometer crystals through dispersing and settling, centrifugation.
Preferably, we are according to 4
oc-8
oc min
-1temperature rise rate progressively heat up.
Further, we more preferably mode be temperature-rise period is divided into two stages, be first warming up to 100-150 DEG C, reaction for some time after, continue to be warming up to 180-230 DEG C, and be obtained by reacting the product containing Pd-Pt alloy nanometer crystals at this temperature.
Wherein, the dehydrated alcohol dispersing and settling of the product after preferred reaction.Wherein the operation of employing dehydrated alcohol dispersing and settling, centrifugation can repeat 3-4 time.
Preferably, the adding proportion that the invention also discloses each component is Pd (NO
3)
2 . 2H
2o 0.1 mol-0.3 mol, H
2ptCl
6 . 6H
2o 0.1 mol-0.3 mol, PVP 10 mmol-15 mmol, CTAB 5mmol-10 mmol, ethylene glycol 30-50 mL.
Further, we give the preferred reaction times is 60-150 min.After temperature reaches the temperature that we expect, homo(io)thermism is kept also to react 60-150 min.For example, after temperature reaches 110-230 DEG C, reaction 60-150 min.For temperature-rise period stage by stage, we are when temperature arrives 100-150 DEG C and 180-230 DEG C of two temperature spot, and control temperature is constant and react 60-150 min respectively.
The present invention further discloses this application of Pd-Pt alloy nanometer crystals in fuel-cell catalyst simultaneously.The particularly application of this Pd-Pt alloy nanometer crystals simultaneously in catalytic oxidation-reduction reaction and oxygen evolution reaction.
Pd-Pt alloy nanometer crystals obtained by the present invention adopts X-ray energy spectrometer (EDS) and X-ray diffractometer (XRD) to characterize its component and structure; Its size, pattern and microstructure etc. are analyzed by transmission electron microscope (TEM) and scanning electronic microscope (STEM).
Pd-Pt alloy nanometer crystals obtained by the present invention has excellent ORR and OER performance, can ORR and OER in efficient catalytic fuel cell.Its performance is better than Pt-C commercially available at present after testing, has important directive significance for renewable energy technologies development.
Pd-Pt alloy nanometer crystals involved in the present invention is prepared by solid liquid phase chemical reaction, Pd-Pt alloy nanometer crystals has controllably been synthesized under normal pressure and lower temperature, simultaneously owing to adopting the mode of " treating different things alike ", temperature programmed control pattern is utilized to obtain having the Pd-Pt alloy nano body of unique concave polyhedron, technique is simple, temperature of reaction is low, and the time is short, is suitable for batch production.
Accompanying drawing explanation
Fig. 1 is the EDS figure of the Pd-Pt alloy nanometer crystals that the present invention synthesizes.
Fig. 2 is the XRD figure of the Pd-Pt alloy nanometer crystals that the present invention synthesizes.
Fig. 3 is the TEM figure of the Pd-Pt alloy nanometer crystals that the present invention synthesizes.
Fig. 4 is the STEM figure of the Pd-Pt alloy nanometer crystals that the present invention synthesizes.
Fig. 5 is the ORR performance test figure of the Pd-Pt alloy nanometer crystals that the present invention synthesizes.
Fig. 6 is the OER performance test figure of the Pd-Pt alloy nanometer crystals that the present invention synthesizes.
Embodiment
Below by specific embodiment, technical solutions according to the invention are further described in detail, but are necessary to point out that following examples are only for the description to summary of the invention, do not form limiting the scope of the invention.
Embodiment 1
Under room temperature, weigh 18 mg(0.03 mmol) (Pd (NO
3)
2 . 2H
2o, 34 mg(0.03 mmol) H
2ptCl
6 . 6H
2o, 110 mg (1 mmol) PVP, 180 mg CTAB(0.5 mmol) powder, and the capacity whole raw material being joined together drying is in the three neck round-bottomed flasks of 250 mL, measuring 20 mL ethylene glycol with graduated cylinder again joins in three neck round-bottomed flasks, ultrasonic and be stirred to and dissolve completely, obtain orange solution.
Three neck round-bottomed flasks are transferred in sand-bath, with after being incubated 60 min under the ramp to 110 of 7 ° of C/min ° C under temperature programmed control, continue to be warming up to 185 ° of C with 7 ° of C/min and be incubated 90 min, to reacting end.Question response device naturally cools to room temperature, adds ethanol in proper amount dispersion, centrifugation solid.Black product is obtained, in vacuum drying oven after dried in vacuo overnight, for analysis and characterization by after solids wash.
Adopt EDS, XRD, TEM and STEM test to analyze product respectively, result as shown in Figures 1 to 4.It is Pd and Pt that Fig. 1 shows principal element, drawing also has the peak of a small amount of C and Cu, carrys out the copper mesh of self-test.Demonstrate 5 sharp-pointed diffraction peaks in Fig. 2, these diffraction peaks are between Emission in Cubic Pd(JCPDS-87-637) and cube Pt(JCPDS-88-2343) between, illustrate that the product obtained is alloy structure.
The Pd-Pt alloy nanometer crystals of a large amount of monodispersed concave polyhedron can be observed from Fig. 3 and Fig. 4.Size is about 13 nm.Therefore, we determine that obtained crystalline product is the Pd-Pt alloy nanometer crystals of concave polyhedron, and crystalline phase is face-centered cubic phase.
Embodiment 2
By cyclic voltammetry and method of polarization curve in three-electrode system, the electrochemical properties of test sample, detailed process is as follows:
Electrochemistry experiment carries out on CHI760e type electrochemical workstation, three electrode test systems of employing standard, the glass-carbon electrode that corresponding working electrode is modified for the sample obtained herein, be platinized platinum to electrode, reference electrode is silver/silver chloride (Ag/AgCl).Electromotive forces all is herein all relative to Ag/AgCl.Electrolytic solution is the KOH solution of 0.1 M.All electro-chemical tests are all 30
ocarry out under C.During each experiment, all modified electrodes are all tested in 0.1 M KOH solution.
The preparation method of sample modified electrode is as follows:
Before each experiment, be the Al that the rotating disk electrode of 5 mm uses 1.0 μm, 0.3 μm and 0.05 μm successively by diameter
2o
3grinding is to minute surface, and then ultrasonic cleaning, finally uses second distillation water wash clean, at room temperature N
2dried for standby under atmosphere.The Pd-Pt alloy nanometer crystals of 2 mg is distributed in 1 mL water, obtains 2 mg mL
-1the suspension of Pd-Pt alloy nanometer crystals.This suspension of 20 μ L and 5 μ L 1% naphthol solution, be successively dispersed in rotating disk electrode surface N
2dry in atmosphere, obtain Pd-Pt alloy nanometer crystals modified electrode.
Before ORR test, first in solution, pass into high-purity O
230 min, and in experimentation, continue logical O
2to keep the O of solution
2atmosphere.The linear time base sweep polarization curve (LSV) that difference is swept under speed is also at O
2carry out in atmosphere, corresponding Electrochemical Scanning speed is 10 mV/s, and sweep limit is-0.80 V-0.20 V.
Before OER test, first in solution, pass into high-purity O
230 min, to remove other gas dissolved in solution, and continue logical O in experimentation
2to keep the O of solution
2atmosphere.LSV is also at O
2carry out in atmosphere, corresponding Electrochemical Scanning speed is 10 mV/s, and speed setting is 1600 rpm, and sweep limit is 0 V-1.0 V.
Detected result is respectively referring to Fig. 5 and Fig. 6.Test result shows, Pd-Pt alloy nanometer crystals shows excellent ORR and OER performance, and from the A-D of Fig. 5, we can see that catalytic activity in catalytic oxidation-reduction reaction of Pd-Pt alloy nanometer crystals that the present invention obtains and stability are better than commercially available Pt/C catalyzer.From Fig. 6, we can see that the present invention obtains the catalytic activity of Pd-Pt alloy nanometer crystals in oxygen evolution reaction and stability is better than commercially available Pt/C catalyzer, thus the Pd-Pt that the present invention obtains is that a kind of performance is far superior to commercially available Pt/C catalyzer, all has the bifunctional electrocatalyst of good behaviour in catalytic oxidation-reduction reaction and oxygen evolution reaction.
Claims (9)
1. a Pd-Pt alloy nanometer crystals, is characterized in that, described Pd-Pt alloy nanometer crystals is concave polyhedron, and its crystalline phase is face-centered cubic phase.
2. a preparation method for Pd-Pt alloy nanometer crystals according to claim 1, is characterized in that, described method is: by Pd (NO
3)
2 . 2H
2o, H
2ptCl
6 . 6H
2o, polyvinylpyrrolidone, cetyl trimethylammonium bromide joins in ethylene glycol solution, is progressively warming up to 110-230 ° of C, and the product be obtained by reacting at this temperature containing Pd-Pt alloy nanometer crystals, obtain Pd-Pt alloy nanometer crystals through dispersing and settling, centrifugation.
3. preparation method according to claim 2, is characterized in that, according to 4-8
oc min
-1temperature rise rate progressively heat up.
4. the preparation method according to Claims 2 or 3, is characterized in that, temperature-rise period is divided into two stages, first 100-150 DEG C is warming up to, after reaction for some time, continue to be warming up to 180-230 DEG C, and be obtained by reacting the product containing Pd-Pt alloy nanometer crystals at this temperature.
5. preparation method according to claim 2, is characterized in that, reacted product dehydrated alcohol dispersing and settling.
6. preparation method according to claim 2, is characterized in that, the adding proportion of each component is Pd (NO
3)
2 . 2H
2o 0.1 mol-0.3 mol, H
2ptCl
6 . 6H
2o 0.1 mol-0.3 mol, PVP 10 mmol-15 mmol, CTAB 5mmol-10 mmol, ethylene glycol 30-50 mL.
7. preparation method according to claim 2, is characterized in that, the reaction times is 60-150 min.
8. the application of Pd-Pt alloy nanometer crystals according to claim 1 in fuel-cell catalyst.
9. application according to claim 8, is characterized in that, described Pd-Pt alloy nanometer crystals is simultaneously in the application of catalytic oxidation-reduction reaction and oxygen evolution reaction.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105903981A (en) * | 2016-05-25 | 2016-08-31 | 南京晓庄学院 | Pd2PtAg nanocrystalline and preparation method and application thereof |
| CN110756819A (en) * | 2019-10-11 | 2020-02-07 | 南京晓庄学院 | Preparation method and application of ruthenium-rhodium alloy nanoring |
Citations (4)
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|---|---|---|---|---|
| JP2008163404A (en) * | 2006-12-28 | 2008-07-17 | Hoya Corp | Alloy nanocrystal, method for producing alloy nanocrystal and fluid dispersion of alloy nanocrystal |
| CN101717071A (en) * | 2009-11-20 | 2010-06-02 | 清华大学 | Method for synthesizing series alloy nanometer crystals |
| CN101772597A (en) * | 2007-05-15 | 2010-07-07 | 魁北克水电公司 | Fe 3Al (Ru) type nanocrystal alloys and nanocrystal form thereof or the manufacturing of non-nano crystalline form are used for the purposes of the electrode of sodium chlorate synthesis |
| CN103668462A (en) * | 2013-11-27 | 2014-03-26 | 浙江大学 | Preparation method of platinum-palladium alloy nanocrystalline |
-
2015
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008163404A (en) * | 2006-12-28 | 2008-07-17 | Hoya Corp | Alloy nanocrystal, method for producing alloy nanocrystal and fluid dispersion of alloy nanocrystal |
| CN101772597A (en) * | 2007-05-15 | 2010-07-07 | 魁北克水电公司 | Fe 3Al (Ru) type nanocrystal alloys and nanocrystal form thereof or the manufacturing of non-nano crystalline form are used for the purposes of the electrode of sodium chlorate synthesis |
| CN101717071A (en) * | 2009-11-20 | 2010-06-02 | 清华大学 | Method for synthesizing series alloy nanometer crystals |
| CN103668462A (en) * | 2013-11-27 | 2014-03-26 | 浙江大学 | Preparation method of platinum-palladium alloy nanocrystalline |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105903981A (en) * | 2016-05-25 | 2016-08-31 | 南京晓庄学院 | Pd2PtAg nanocrystalline and preparation method and application thereof |
| CN110756819A (en) * | 2019-10-11 | 2020-02-07 | 南京晓庄学院 | Preparation method and application of ruthenium-rhodium alloy nanoring |
| CN110756819B (en) * | 2019-10-11 | 2020-11-10 | 南京晓庄学院 | Preparation method and application of ruthenium-rhodium alloy nanoring |
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