CN104451782A - Octahedral platinum nanoparticles as well as synthesis method and application thereof - Google Patents
Octahedral platinum nanoparticles as well as synthesis method and application thereof Download PDFInfo
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- CN104451782A CN104451782A CN201410719673.2A CN201410719673A CN104451782A CN 104451782 A CN104451782 A CN 104451782A CN 201410719673 A CN201410719673 A CN 201410719673A CN 104451782 A CN104451782 A CN 104451782A
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Abstract
The invention discloses an electrochemical synthesis method of octahedral platinum nanoparticles. The octahedral platinum nanoparticles are synthesized by electrochemically depositing a mixed solution of chloroplatinic acid for 500 seconds at the deposition potential of -0.2V according to amperometric I-t curves by adopting a CHI660D electrochemical workstation, a working electrode, a reference electrode and a counter electrode, wherein the glassy carbon electrode serves as the working electrode, the Ag/AgCl electrode serves as the reference electrode, and the platinum wire electrode serves as the counter electrode. The electrochemical synthesis method of the octahedral platinum nanoparticles is easy to operate and has good reproducibility, and the prepared octahedral platinum nanoparticles are stable and have high methanol catalyzing activity.
Description
Technical field
The invention belongs to fuel cell field, specifically a kind of employing is simple to operate, and the nano platinum particle of the electrochemical techniques method synthesizing octahedral structure that circulation ratio is high, for catalysis methanol oxidizing reaction.
Background technology
Fuel cell have energy transformation ratio high, pollute the features such as little, applied widely, load responding is fast, be used as automobile power power supply, communication base station power supply, standby power supply and laptop computer field of power supplies there is good development prospect.
In fuel cell, platinum catalyst is the electrocatalyst materials be most widely used.But the scarcity of its high cost and resource is generally considered as the biggest obstacle of commercializing fuel cells.Therefore, the eelctro-catalyst of research novel high-performance, low cost is needed badly.Performance and electrocatalysis material form and dispersity closely related, in the past in 10 years, people nano-catalyst material composition and size controlling in achieve impressive progress.In addition, catalytic performance is also closely related with the pattern (namely surperficial crystal face or surface atom arrange) of particle.Recent years, design and develop the research emphasis that the eelctro-catalyst of novel special appearance and related basic research thereof become fuel cell electro-catalyst.The catalysis of nano platinum particle to methyl alcohol of octahedral structure has very high activity.
The preparation of metal platinum nano material can be divided into physical preparation method and chemical preparation process from large aspect.Physical preparation method adopts the technology such as optical, electrical that material is evaporated in vacuum or inert atmosphere, then makes atom or molecule form the ultrafine particle of nanoscale.Chemical preparation process prepares metal nanoparticle by the nucleation of atoms metal, growth.Such as, the part reduction of chemical reduction method, electrochemical reducing, thermal decomposition method, photochemical breakdown method, sonochemistry decomposition method, organometallic compound and substitution method etc.The distribution of sizes of the metal nanoparticle that usual physical preparation method obtains is wider, chemical preparation process then can by change the kind of the molar ratio of reductive agent and metal-salt, reductive agent and tensio-active agent, temperature of reaction, solution the condition such as pH value carry out more effectively to control the size and dimension of metal nanoparticle.Therefore chemical preparation process is the main method preparing metal nanoparticle.
Up to now, at home and abroad there is no employing simple to operate, the nano platinum particle of the electrochemical techniques method synthesizing octahedral structure of favorable reproducibility.So invention one has simple to operate, favorable reproducibility, the nano platinum particle preparation method of nanoparticles stable is an important technological problems in the urgent need to address.
Summary of the invention
The object of the invention is by simple to operate, the electrochemical techniques of favorable reproducibility prepare nanoparticles stable, to the nano platinum particle of the active high octahedral structure of methanol oxidation.
The object of the present invention is achieved like this:
Octahedral structure nano platinum particle electrochemical method for synthesizing and a methanol oxidation application thereof, comprise the following steps:
(1) Platinic chloride mixing solutions is prepared: get 18.0 ~ 20.0mmol/L Platinic chloride (H
2ptCl
6), add Repone K (KCl) solid wherein, make Platinic chloride mixing solutions concentration reach 19.0 ~ 25.0mmol/L, adding Brij58 tensio-active agent to its massfraction is again 0.7% ~ 1.2%, stir, leave standstill, put into the preservation of 4 DEG C, refrigerator;
(2) glass-carbon electrode is successively carried out sanding and polishing with the alumina powder of 0.3 micron and 0.05 micron respectively, then use deionized water respectively, ethanol and deionized water clean glass-carbon electrode;
(3) CHI660D electrochemical workstation and three-electrode system is adopted to carry out electrochemical deposition synthesis nano platinum particle: using glass-carbon electrode as working electrode, Ag/AgCl electrode is as reference electrode, platinum wire electrode is as to electrode, adopt ampere i-t curve method, with the condition of sedimentation potential-0.2V and depositing time 500s, carry out the above-mentioned Platinic chloride mixing solutions of electrochemical deposition, synthesis nano platinum particle, then drip the Nafion solution of 1% of 10 microlitres, dry for subsequent use under room temperature.
The catalysis of nano platinum particle to methyl alcohol and formic acid of octahedral structure has higher activity.Adopt simple to operate, reproducible electrochemical techniques prepare nanoparticles stable, to the active high octahedral structure nano platinum particle of methanol oxidation.Observed the pattern of nanoparticle under differential responses condition by field emission scanning electron microscope (SEM), and investigate the catalytic activity of nano platinum particle to methyl alcohol of different-shape.Experimental result shows, adopts I-t curve electrochemical method, at sedimentation potential-0.2V, under depositing time 500s condition, obtains the nano platinum particle of octahedral structure, and compared with the nano platinum particle prepared under other conditions, the highest to the catalytic activity of methyl alcohol.
Accompanying drawing explanation
The nano platinum particle modified electrode of the different depositing time synthesis of Fig. 1 is at 0.5M H
2sO
4, the cyclic voltammetry curve figure in 1.0M methanol solution.
The SEM figure of the nano platinum particle of the different depositing time synthesis of Fig. 2, A-100s, B-200s, C-300s, D-400s, E-500s, F-600s (depositing time).
The nano platinum particle modified electrode of the different sedimentation potential synthesis of Fig. 3 is at 0.5M H
2sO
4, the cyclic voltammetry curve figure in 1.0M methanol solution.
Fig. 4 octahedral structure modified glassy carbon electrode and commercial nano platinum particle modified glassy carbon electrode are at 0.5M H
2sO
4, the cyclic voltammetry curve figure in 1.0M methanol solution.
Fig. 5 octahedral structure modified glassy carbon electrode and commercial nano platinum particle modified glassy carbon electrode are at 0.5M H
2sO
4cyclic voltammetry curve figure in solution.
Embodiment
The present invention's experiment carries out on electrochemistry CHI 660D type electrochemical workstation (Shanghai Chen Hua Instrument Ltd.); Field emission scanning electron microscope spectrum adopts Hitachi S – 4800 (Tokyo, Japan) field emission scanning electron microscope, SK2200H ultrasonic apparatus (Shanghai High Kudos Science Instrument Co., Ltd.).
Below by embodiment, the present invention will be further described.
Measure 18.0 ~ 20.0mmol/L Platinic chloride (H
2ptCl
6) 3.0 ~ 5.0mL, in platinum acid chloride solution, add Repone K (KCl) solid, make its concentration reach 19.0 ~ 25.0mmol/L.In this mixing solutions, add Brij58 tensio-active agent to its massfraction is 0.7% ~ 1.2%, stirs and makes it even, then leave standstill certain hour, be then placed in 4 DEG C of refrigerators and preserve, for subsequent use.Be that the glass-carbon electrode of 3 millimeters successively carries out sanding and polishing with the alumina powder of 0.3 micron and 0.05 micron respectively by diameter, then use deionized water respectively, ethanol and deionized water clean glass-carbon electrode.CHI660D electrochemical workstation and three-electrode system is adopted to carry out electrochemical deposition synthesis nano platinum particle.Using glass-carbon electrode as working electrode, Ag/AgCl electrode is as reference electrode, and platinum wire electrode is as to electrode.Adopt ampere i-t curve method, with the condition of sedimentation potential-0.2V and depositing time 500s, carry out the above-mentioned Platinic chloride mixing solutions of electrochemical deposition, synthesizing octahedral structure nano platinum particle.Then drip the Nafion solution of 1% of 10 microlitres, dry for subsequent use under room temperature.
The nano platinum particle synthesized under different depositing time conditions is on the impact of the catalytic performance of methyl alcohol:
Fig. 1 is the H at 0.5M
2sO
4, in 1.0M methyl alcohol, sedimentation potential-0.2V and different depositing time synthesis nano platinum particle modified glassy carbon electrode to the catalytic cycle volt-ampere curve figure of methyl alcohol.Can obviously be found out by Fig. 1, under-0.2V sedimentation potential, the catalytic performance of nano platinum particle to methyl alcohol that depositing time 500s synthesizes is the highest.Meanwhile, in order to observe the pattern of the nano platinum particle of different depositing time synthesis to the impact of methanol oxidation performance, in experimentation, field emission scanning electron microscope (SEM) is adopted to carry out morphology characterization to nano platinum particle modified electrode.
Fig. 2 A-F is the nano platinum particle SEM morphology characterization figure synthesized under different depositing time condition, as can be seen from the figure, when being when deposited 100s, the shape major part of nanoparticle is ball-shaped and size of particles is less, the nanoparticle that there is small portion is octahedral structure, but the octahedra volume formed comparatively large (diameter is about 1 μm).Depositing time is from 100s ~ 400s, and the nanostructure major part of formation is all spheroidal, just there will be the nano platinum particle of octahedral structure under only having 100s and 300s depositing time condition.Be under 500s and 600s condition when deposited, the Nanoparticle shape of synthesis is almost octahedral structure, and the about 500nm of particle dia.The nano platinum particle surface ratio of synthesizing under 500s condition is more coarse, edge defectiveness.The nano platinum particle synthesized under 600s condition has some particles to be stacked, and may reduce active surface area.
Can be inferred by Fig. 1 data, surface is more coarse, and the nano platinum particle display of the defective octahedral structure in edge is higher to the catalytic performance of methyl alcohol.Experimental data shows, the nano platinum particle of octahedral structure is higher than the catalytic performance of spherical nano platinum particle to methyl alcohol.
The nano platinum particle of different sedimentation potential synthesis is on the impact of methanol oxidation performance:
Ampere I-t curve method is the method for a kind of constant potential reduction metal ions.
Fig. 3 is the H at 0.5M
2sO
4in 1.0M methyl alcohol, the nano platinum particle modified glassy carbon electrode of different sedimentation potential synthesis, to the catalytic cycle volt-ampere curve figure of methyl alcohol, obviously shows from Fig. 3, under sedimentation potential-0.2V condition, the catalytic performance of nano platinum particle modified electrode to methyl alcohol of synthesis is the highest.
Fig. 4 and Fig. 5 is contrast experiment.
Fig. 4 is that octahedral structure nano platinum particle modified glassy carbon electrode and commercial nano platinum particle modified glassy carbon electrode are at 0.5M H
2sO
4, carry out cyclic voltammetry experiment in 1.0M methyl alcohol, obviously find out, the nano platinum particle of octahedral structure is to the catalytic activity height of methyl alcohol and commercial nano platinum particle.
Fig. 5 is that two kinds of different modifying electrodes are at 0.5M H
2sO
4carry out cyclic voltammetry experiment, as can be seen from experimental result, the active surface area of the glass-carbon electrode that octahedral structure nano platinum particle is modified is higher than the glass-carbon electrode of commercial nano platinum particle modification.
Claims (3)
1. an octahedral structure nano platinum particle electrochemical deposition synthetic method, is characterized in that, comprise the following steps:
(1) Platinic chloride mixing solutions is prepared: get 18.0 ~ 20.0mmol/L Platinic chloride, add solid potassium chloride wherein, Platinic chloride mixing solutions concentration is made to reach 19.0 ~ 25.0mmol/L, adding Brij58 tensio-active agent to its massfraction is again 0.7% ~ 1.2%, stir, leave standstill, put into the preservation of 4 DEG C, refrigerator;
(2) glass-carbon electrode is successively carried out sanding and polishing with the alumina powder of 0.3 micron and 0.05 micron respectively, then use deionized water respectively, ethanol and deionized water clean glass-carbon electrode;
(3) CHI660D electrochemical workstation and three-electrode system is adopted to carry out electrochemical deposition synthesis nano platinum particle: using glass-carbon electrode as working electrode, Ag/AgCl electrode is as reference electrode, platinum wire electrode is as to electrode, adopt ampere i-t curve method, with the condition of sedimentation potential-0.2V and depositing time 500s, electrochemical-deposition step (1) gained Platinic chloride mixing solutions, synthesis nano platinum particle.
2. the nano platinum particle of octahedral structure prepared of electrochemical deposition synthetic method according to claim 1.
3. the nano platinum particle of octahedral structure according to claim 2 is used for catalysis methanol oxidizing reaction.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107482231A (en) * | 2017-08-01 | 2017-12-15 | 江苏理工学院 | A kind of spherical Pt/ charings stalk compound material of fine and close three-dimensional manometer and preparation method thereof |
| CN107845816A (en) * | 2017-10-23 | 2018-03-27 | 济南大学 | A kind of coarse shape of octahedron PtCoFe alloy particles and preparation method thereof |
| CN107845817A (en) * | 2017-10-23 | 2018-03-27 | 济南大学 | A kind of method using coarse shape of octahedron PtCoFe nanocatalysts catalysis oxidation formic acid electrochemistry |
| CN107845815A (en) * | 2017-10-23 | 2018-03-27 | 济南大学 | A kind of implementation method for being used to improve methanol fuel cell electrooxidation activity |
| CN113224324A (en) * | 2021-07-08 | 2021-08-06 | 成都大学 | Palladium-doped aluminum-cobalt-chromium-iron-nickel high-entropy alloy composite electrode and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107482231A (en) * | 2017-08-01 | 2017-12-15 | 江苏理工学院 | A kind of spherical Pt/ charings stalk compound material of fine and close three-dimensional manometer and preparation method thereof |
| CN107845816A (en) * | 2017-10-23 | 2018-03-27 | 济南大学 | A kind of coarse shape of octahedron PtCoFe alloy particles and preparation method thereof |
| CN107845817A (en) * | 2017-10-23 | 2018-03-27 | 济南大学 | A kind of method using coarse shape of octahedron PtCoFe nanocatalysts catalysis oxidation formic acid electrochemistry |
| CN107845815A (en) * | 2017-10-23 | 2018-03-27 | 济南大学 | A kind of implementation method for being used to improve methanol fuel cell electrooxidation activity |
| CN107845817B (en) * | 2017-10-23 | 2019-06-21 | 济南大学 | A method of using coarse shape of octahedron PtCoFe nanocatalyst catalysis oxidation formic acid electrochemistry |
| CN107845815B (en) * | 2017-10-23 | 2019-08-09 | 济南大学 | It is a kind of for improving the implementation method of methanol fuel cell electrooxidation activity |
| CN113224324A (en) * | 2021-07-08 | 2021-08-06 | 成都大学 | Palladium-doped aluminum-cobalt-chromium-iron-nickel high-entropy alloy composite electrode and preparation method thereof |
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