CN100421787C - Platinum icosahedron nano crystal catalyst, its preparing method and use - Google Patents
Platinum icosahedron nano crystal catalyst, its preparing method and use Download PDFInfo
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Abstract
The invention relates to a platinum icositetrahedron nm crystal catalyst and preparation method and application, relates to a nm catalyst and preparation method.It supplies a platinum icositetrahedron nm crystal catalyst and preparation method and application in fuel cells, electrochemical synthesis. It is a platinum nm crystal catalyst, with icositetrahedron; its surface is composed of high index crystal face structure of index (210)-(410). In preparation, first prepared the platinum nm particle by electrodeposit method; and treated the square wave potentials of the platinum nm particle on the basement: used the basement of electrodeposition platinum nm particles as a working electrode, working electrode and reference electrode add to the sulfuric acid solution containing additives, imposed square potential on the two electrodes, upper limit electric potential is 0.90 to 1.30V, the minimum potential is -0.30 to10V, the frequency is 1Hz to 1KHz, obtained the grain size of 5-300nm of the platinum icositetrahedron nm crystal catalyst.
Description
Technical field
The present invention relates to a kind of nanocatalyst and preparation method thereof, particularly relate to a kind of platinum icosahedron nano crystal catalyst and preparation method thereof, and its application in key areas such as fuel cell, electricity be synthetic.
Background technology
The platinum nano material is a widely used catalyst in the key areas such as fuel cell, electricity be synthetic, has obtained further investigation over nearly 20 years.Further improve the performance of platinum nano catalyst and the key issue that utilization ratio is this field.Improving the activity of nanocatalyst can form by regulating it, the more important thing is the shape that changes catalyst nanoparticles, and promptly the control surface atomic arrangement structure is realized (referring to document: Nano Lett., 2004,4:1343-1348; Electrochem.Commun., 2004,6:1080-1084).
The shape of the nano platinum particle in the existing platinum nanocrystal catalyst mainly is cuboctahedron, cube etc., its surface be 111}, two kinds low index crystal faces of 100} (referring to document: Science, 1996,272:1924-1926).The basic research of monocrystalline model electro-catalysis points out that the catalytic activity of high index crystal face and stability obviously are better than low index crystal face (referring to document: Nature, 1975,258:580-583; J.Electroanal.Chem., 1992,340:213-226).Therefore, the preparation surface is to significantly improve nanocatalyst active and stable key and important channel for the nanocrystal of high index crystal plane structure.But, because in catalyst preparation process, the speed of growth of high index crystal face far is tending towards faster than low index crystal face disappearing, therefore general chemical synthesis process can't be prepared the nanocrystal of high index crystal plane structure (referring to document: Crystal growth, 1951, New York:Wiley).Up to now, never see the report of relevant metal icosahedron nano crystal.
Summary of the invention
The object of the present invention is to provide a kind of platinum icosahedron nano crystal catalyst and preparation method thereof.
Another object of the present invention is to provide the application of relevant platinum icosahedron nano crystal catalyst in key areas such as fuel cell, electricity be synthetic.
Platinum icosahedron nano crystal catalyst of the present invention is a kind of platinum nanocrystal catalyst, and it is shaped as tetrahexahedron, and the surface of tetrahexahedron is that high index crystal plane structure between (210)～(410) is formed by index.
The preparation method of platinum icosahedron nano crystal catalyst of the present invention may further comprise the steps:
1) on the inert electrode material substrate, adopt electro-deposition method to prepare nano platinum particle.
2) nano platinum particle on the inert electrode material substrate being carried out the square wave current potential handles: the substrate of nano platinum particle is arranged as working electrode with electro-deposition, working electrode and reference electrode are put into the sulfuric acid solution that contains 0～100mM additive, apply the square wave current potential at working electrode and reference electrode, the upper limit current potential of square wave is 0.90～1.30V, the lower limit current potential is-0.30～0.10V, square wave frequency is 1Hz～1KHz, and getting particle diameter is the platinum icosahedron nano crystal catalyst of 5～300nm.
Described inert electrode material is selected from a kind of in glass carbon, electro-conductive glass, graphite, pyrolytic graphite, high order pyrolytic graphite and the active carbon.Described on the inert electrode material substrate, adopt electro-deposition method prepare nano platinum particle can be at first with the inert electrode material substrate as working electrode, with the saturated calomel electrode is reference electrode, working electrode and reference electrode are put into platinum plating solution, between working electrode and reference electrode, apply the square wave current potential, the upper limit current potential of square wave is 0.50～0.80V, the lower limit current potential is 0.10～0.30V, square wave frequency is 10～100Hz, make nano platinum particle, the particle diameter of nano platinum particle is about 200～1000nm.Platinum plating solution can adopt the platinum plating solution that contains potassium chloroplatinate and sulfuric acid solution, preferably adopts the platinum plating solution that contains 2mM potassium chloroplatinate and 0.5M sulfuric acid solution.
In step 2) in, reference electrode is a saturated calomel electrode, generally adopts the current potential between potentiostat control working electrode and the reference electrode.Additive can be selected a kind of in ascorbic acid, citric acid, glucose and the polyvinylpyrrolidone (PVP) for use.
Platinum icosahedron nano crystal catalyst can be used as eelctro-catalyst and is used for fuel cell, can obviously improve the cell voltage of fuel cell.Platinum icosahedron nano crystal catalyst can be used as eelctro-catalyst and is used for having dynamo-electric synthesizing, and can obviously improve has dynamo-electric synthetic speed.
Compare with existing platinum nanocrystal catalyst, the present invention has following outstanding advantage:
1. platinum icosahedron nano crystal catalyst catalytic activity height not only, heat endurance and chemical stability are good, and the oxidation reaction to organic molecules such as formic acid and ethanol in fuel cell shows excellent catalytic activity; And the high conformity of its crystalline form, crystalline form is attractive in appearance.
2. the surface of platinum icosahedron nano crystal catalyst is that high index crystal plane structure between (210)～(410) is formed by index, because the catalytic activity of high index crystal face apparently higher than low index crystal face, has therefore determined the catalytic activity of the platinum icosahedron nano crystal catalyst of the present invention's preparation will significantly be better than existing platinum nanocrystal catalyst.
3. the particle size of platinum icosahedron nano crystal catalyst is controlled, and particle diameter can be regulated and control in the scope of 5～300nm.
4. the preparation method of platinum icosahedron nano crystal catalyst is simple.
5. platinum icosahedron nano crystal catalyst can be widely used in key areas such as fuel cell, electricity be synthetic.
Description of drawings
Fig. 1 is ESEM (SEM) figure of the platinum icosahedron nano crystal catalyst of preparation in the embodiment of the invention 1.
Fig. 2 is ESEM (SEM) figure of the platinum icosahedron nano crystal catalyst of preparation in the embodiment of the invention 2.
Fig. 3 is the catalytic activity phenogram of the platinum icosahedron nano crystal catalyst of preparation in the embodiment of the invention 3 to formic acid.In Fig. 3, abscissa is working electrode current potential E/V (SCE is a reference electrode with the saturated calomel electrode), and ordinate is current density, J/mA cm
-2The Pt/C nanometer crystal catalyst (platinum content is 20wt%) that curve a and b difference platinum icosahedron nano crystal catalyst and U.S. E-TEK company produce.Solution during measurement is 0.25M formic acid and 0.5M sulfuric acid.
Fig. 4 is the catalytic activity phenogram of the platinum icosahedron nano crystal catalyst of preparation in the embodiment of the invention 4 to ethanol.In Fig. 4, abscissa is working electrode current potential E/V (SCE is a reference electrode with the saturated calomel electrode), and ordinate is current density, J/mA cm
-2The Pt/C nanometer crystal catalyst (platinum content is 20wt%) that curve a and b difference platinum icosahedron nano crystal catalyst and U.S. E-TEK company produce.Solution during measurement is 0.1M ethanol and 0.1M perchloric acid.
The specific embodiment
The embodiment that below provides will the present invention is further illustrated in conjunction with the accompanying drawings.
Embodiment 1: the preparation nano platinum particle: with glass carbon (diameter is 6mm) substrate as working electrode, with the saturated calomel electrode is reference electrode, working electrode and reference electrode are put into the platinum plating solution that contains 2mM potassium chloroplatinate and 0.5M sulfuric acid, between working electrode and reference electrode, apply the square wave current potential and carry out electro-deposition, the upper limit current potential of square wave is 0.50V, and the lower limit current potential is 0.10V, and square wave frequency is 10Hz, time is 40min, makes the 1000nm nano platinum particle.The preparation platinum icosahedron nano crystal catalyst: with the glass carbon substrate of supported platinum nano particle as working electrode, with the saturated calomel electrode is reference electrode, working electrode and reference electrode are put into the 0.1M sulfuric acid solution that contains the 100mM ascorbic acid, between working electrode and reference electrode, apply the square wave current potential and carry out electrochemical treatments.The upper limit current potential of square wave is 1.30V, and the lower limit current potential is-0.10V, and square wave frequency is 100Hz, and the processing time is 60min, makes the platinum icosahedron nano crystal catalyst that particle diameter is about 200nm.Fig. 1 is the SEM figure of prepared platinum nanocrystal catalyst, and platinum nanocrystal catalyst is perfect tetrahexahedron shape as seen from Figure 1.
Embodiment 2: similar with the process of embodiment 1, but when the preparation nano platinum particle, the upper limit current potential of square wave is 0.80V, and the lower limit current potential is 0.30V, and square wave frequency is 50Hz, and the time is 20min, makes the nano platinum particle of about 400nm.When the preparation platinum icosahedron nano crystal catalyst, solution is not for containing the 0.1M sulfuric acid of additive.The upper limit current potential of square wave is 1.0V, and the lower limit current potential is-0.20V, and square wave frequency is 50Hz, and the processing time is 10min, makes the platinum icosahedron nano crystal catalyst that particle diameter is about 20nm.Fig. 2 is the SEM figure of platinum nanocrystal catalyst, and platinum nanocrystal catalyst still keeps the shape of tetrahexahedron as seen from Figure 2.
Embodiment 3: similar with the process of embodiment 1, but when the preparation nano platinum particle, the upper limit current potential of square wave is 0.70V, and the lower limit current potential is 0.20V, and square wave frequency is 50Hz, and the time is 40min, makes the nano platinum particle of 700nm.When the preparation platinum icosahedron nano crystal catalyst, solution is the 0.1M sulfuric acid that contains the 30mM ascorbic acid.The upper limit current potential of square wave is 1.10V, and the lower limit current potential is-0.30V, and square wave frequency is 20Hz, and the processing time is 30min, makes platinum icosahedron nano crystal catalyst.Fig. 3 is the catalytic activity phenogram of platinum icosahedron nano crystal catalyst (Pt THH) to formic acid, shows that the catalytic activity of its per surface area obviously is better than the commercialization platinum nanocrystal catalyst E-TekPt/C (20wt%) of U.S. E-TEK company.
Embodiment 4: similar with the process of embodiment 1, but when the preparation platinum icosahedron nano crystal catalyst, solution is the 0.1M sulfuric acid that contains the 30mM natrium citricum.The lower limit current potential of square wave is-0.20V, and square wave frequency is 20Hz, and the processing time is 30min, makes platinum icosahedron nano crystal catalyst.Fig. 4 is the catalytic activity phenogram of platinum icosahedron nano crystal catalyst to ethanol, shows that the catalytic activity of its per surface area obviously is better than the commercialization platinum nanocrystal catalyst of U.S. E-TEK company.
Embodiment 5: similar with the process of embodiment 2, but in preparation during nano platinum particle, the frequency of square wave is made as 100Hz, and the time is 10min, makes the nano platinum particle of about 200nm.When the preparation platinum icosahedron nano crystal catalyst, the upper limit current potential of square wave is elected 0.90V as, and the processing time is 3min, can make the platinum icosahedron nano crystal catalyst of particle diameter less than 10nm.
Embodiment 6: similar with the process of embodiment 3, but when the preparation platinum icosahedron nano crystal catalyst, the lower limit current potential of square wave is elected 0.10V as, and the processing time is 30min, can make the platinum icosahedron nano crystal catalyst of about 50nm.
Embodiment 7: similar with the process of embodiment 1, but when the preparation platinum icosahedron nano crystal catalyst,, can make platinum icosahedron nano crystal catalyst with the frequency 1Hz of square wave.
Embodiment 8: similar with the process of embodiment 1, but when the preparation platinum icosahedron nano crystal catalyst, solution is the 0.1M sulfuric acid that contains 100mM glucose, the frequency 100Hz of square wave can make platinum icosahedron nano crystal catalyst.
Embodiment 9: similar with the process of embodiment 1, but when the preparation platinum icosahedron nano crystal catalyst, solution can make platinum icosahedron nano crystal catalyst for containing the 0.1M sulfuric acid of 20mM polyvinylpyrrolidone (PVP).
Embodiment 10: similar with the process of embodiment 1, but replace the glass carbon substrate with the ITO electro-conductive glass, can make platinum icosahedron nano crystal catalyst.
Embodiment 11: similar with the process of embodiment 1, but replace the glass carbon substrate with graphite, can make platinum icosahedron nano crystal catalyst.
Embodiment 12: similar with the process of embodiment 1, but replace the glass carbon substrate with pyrolytic graphite, can make platinum icosahedron nano crystal catalyst.
Embodiment 13: similar with the process of embodiment 1, but replace the glass carbon substrate with high order pyrolytic graphite (HOPG), can make platinum icosahedron nano crystal catalyst.
Embodiment 14: similar with the process of embodiment 1, but replace the glass carbon substrate with the active carbon of paraffin bonding, can make platinum icosahedron nano crystal catalyst.
Claims (10)
1. platinum icosahedron nano crystal catalyst is characterized in that this catalyst is a kind of platinum nanocrystal catalyst, and it is shaped as tetrahexahedron, and the surface of tetrahexahedron is that high index crystal plane structure between (210)～(410) is formed by index.
2. the preparation method of platinum icosahedron nano crystal catalyst as claimed in claim 1 is characterized in that may further comprise the steps:
1) on the inert electrode material substrate, adopt electro-deposition method to prepare nano platinum particle;
2) nano platinum particle on the inert electrode material substrate being carried out the square wave current potential handles: the substrate of nano platinum particle is arranged as working electrode with electro-deposition, working electrode and reference electrode are put into the sulfuric acid solution that contains 0～100mM additive, apply the square wave current potential at working electrode and reference electrode, the upper limit current potential of square wave is 0.90～1.30V, the lower limit current potential is-0.30～0.10V, square wave frequency is 1Hz～1KHz, gets platinum icosahedron nano crystal catalyst.
3. the preparation method of platinum icosahedron nano crystal catalyst as claimed in claim 2 is characterized in that described inert electrode material is selected from a kind of in glass carbon, electro-conductive glass, graphite and the active carbon.
4. the preparation method of platinum icosahedron nano crystal catalyst as claimed in claim 2, it is characterized in that described on the inert electrode material substrate, adopt electro-deposition method prepare nano platinum particle be at first with the inert electrode material substrate as working electrode, with the saturated calomel electrode is reference electrode, working electrode and reference electrode are put into platinum plating solution, between working electrode and reference electrode, apply the square wave current potential, the upper limit current potential of square wave is 0.50～0.80V, the lower limit current potential is 0.10～0.30V, square wave frequency is 10～100Hz, makes nano platinum particle.
5. the preparation method of platinum icosahedron nano crystal catalyst as claimed in claim 4 is characterized in that platinum plating solution is the platinum plating solution that contains potassium chloroplatinate and sulfuric acid solution.
6. the preparation method of platinum icosahedron nano crystal catalyst as claimed in claim 5 is characterized in that platinum plating solution is the platinum plating solution that contains 2mM potassium chloroplatinate and 0.5M sulfuric acid solution.
7. the preparation method of platinum icosahedron nano crystal catalyst as claimed in claim 2 is characterized in that in step 2) in, reference electrode is a saturated calomel electrode.
8. the preparation method of platinum icosahedron nano crystal catalyst as claimed in claim 2 is characterized in that additive is selected from a kind of in ascorbic acid, citric acid, glucose and the polyvinylpyrrolidone.
9. platinum icosahedron nano crystal catalyst as claimed in claim 1 is as the application of eelctro-catalyst in fuel cell.
10. platinum icosahedron nano crystal catalyst as claimed in claim 1 as eelctro-catalyst in the application that has in dynamo-electric synthetic.
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| CN101928979B (en) * | 2010-08-06 | 2012-07-04 | 厦门大学 | Surface structure regulation, control and preparation method of metallic nanocatalyst |
| CN102268262B (en) * | 2011-05-25 | 2013-05-22 | 云南大学 | Method for synthesizing Pt: ZnSe(S) alloy nano crystal by aqueous phase process |
| CN102211198B (en) * | 2011-05-25 | 2013-05-22 | 云南大学 | Method for synthesizing water-soluble Pt: ZnSe(S) alloyed nanometer crystal by using hydro-thermal method |
| CN103074641B (en) * | 2012-12-28 | 2016-06-01 | 上海交通大学 | The preparation method of the Pt/ITO electrode of efficient electric catalytic oxidation ammonia |
| CN105664927A (en) * | 2015-12-30 | 2016-06-15 | 厦门大学 | Carbon-paper-supported high-index crystal face platinum nano particle catalyst, preparation method and application thereof |
| CN111534833B (en) * | 2020-04-08 | 2021-08-17 | 北京化工大学 | Copper nano electrode with high-index crystal face and preparation method and application thereof |
| CN112156788B (en) * | 2020-07-28 | 2021-11-12 | 中南大学 | Quaternary Ni-Fe-W-Mo alloy high-efficiency oxygen evolution electrocatalyst and preparation method and application thereof |
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| US20010009119A1 (en) * | 1999-07-26 | 2001-07-26 | International Business Machines Corporation | Chemical synthesis of monodisperse and magnetic alloy nanocrystal containing thin films |
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| US20010009119A1 (en) * | 1999-07-26 | 2001-07-26 | International Business Machines Corporation | Chemical synthesis of monodisperse and magnetic alloy nanocrystal containing thin films |
| CN1685071A (en) * | 2002-09-30 | 2005-10-19 | 株式会社那诺技术研究所 | Tenacious metallic nano-crystalline bulk material with high hardness and high strength, and its manufacturing method |
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