CN102773093A - Green synthetic method for dendritic platinum nanocluster electrocatalyst - Google Patents

Green synthetic method for dendritic platinum nanocluster electrocatalyst Download PDF

Info

Publication number
CN102773093A
CN102773093A CN2011101199771A CN201110119977A CN102773093A CN 102773093 A CN102773093 A CN 102773093A CN 2011101199771 A CN2011101199771 A CN 2011101199771A CN 201110119977 A CN201110119977 A CN 201110119977A CN 102773093 A CN102773093 A CN 102773093A
Authority
CN
China
Prior art keywords
platinum
triblock copolymer
pluronic
cluster
ptcl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2011101199771A
Other languages
Chinese (zh)
Other versions
CN102773093B (en
Inventor
张丽娟
王岩
李钒
王艳飞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Technology
Original Assignee
Beijing University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing University of Technology filed Critical Beijing University of Technology
Priority to CN201110119977.1A priority Critical patent/CN102773093B/en
Publication of CN102773093A publication Critical patent/CN102773093A/en
Application granted granted Critical
Publication of CN102773093B publication Critical patent/CN102773093B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a green synthetic method for a dendritic platinum nanocluster electrocatalyst, and belongs to the technical field of platinum nanocatalyst. The synthetic method comprises the following steps of (1) dispersing a platinum precursor and a triblock copolymer in distilled water to make a solution with a molar ratio of 2-50 : 1; (2) ultrasonic dispersing to make the triblock copolymer and the platinum precursor mixed uniformly; (3) standing to make the triblock copolymer and ions of the platinum precursor fully adsorbed in a coordination manner; and (4) putting in a water bath with a temperature of 80-100 DEG C and heating for 2-48 hours, and thus the dendritic platinum nanocluster is obtained. The dendritic platinum nanocluster prepared by the method has high yield, high purity, uniform morphology and good dispersibility. The dendritic platinum nanocluster has relatively high specific surface area, can effectively improve electrocatalytic efficiency, has relatively high stability and durability, is simple in operation of preparation process, has strong controllability, and is helpful for industrialized production.

Description

A kind of green synthesis method of dendroid platinum nano-cluster eelctro-catalyst
Technical field
The invention belongs to the platinum nano catalyst technical field, relate to the platinum group nanometer fuel battery catalyst preparation technical field of high electrocatalytic active, relate in particular to a kind of green synthesis method of dendroid platinum nano-cluster.
Background technology
Fuel cell has the energy conversion efficiency height, and cleanliness without any pollution, eco-friendly advantage are considered to first-selected generation technology of 21 century.The platinum group nanocatalyst has superior electrocatalysis characteristic and superpower resistance to corrosion is used widely aspect fuel cell.But, stablize the research and development of the platinum group nanocatalyst of durability because soaring to the increasing progressively of platinum demand, price greatly promoted economical and efficient property.
The platinum group nanocatalyst of the synthetic high electrocatalytic active of morphology control is that the research of fuel cell is popular always.Characteristics such as that dendroid platinum group nanocatalyst of the present invention has is polygonal, polygon, polycrystalline face, many defectives, because of its high-specific surface area, many reactivities point can improve electro catalytic activity and utilization rate, shows potential using value.
The preparation method of the nano-metal particle of report adopts liquid-phase reduction metal ion or pyrolytic metallo-organic compound more at present.Reagent in three steps of liquid phase reduction all should be assessed from the angle of Green Chemistry: 1. select suitable solvent 2. to adopt eco-friendly reducing agent 3. to use nontoxic dispersant and stabilizing agent.
The Basic Ways of preparation nano platinum particle is the reduction chloroplatinic acid at present; 1. solvent commonly used has the mixing material, distilled water of ionic liquid, hydration alcohol etc.; But ion liquid cost is higher, and the aqueous solution is considered to the solvent of environmental friendliness and economical and efficient and is used widely; 2. reducing agent commonly used has: ethanol, ethylene glycol, hydrazine hydrate, sodium borohydride, dimethyl formamide, formaldehyde etc., find through various index evaluation analysis, the reproducibility of alcohols a little less than, required condition is harsh; Though reproducibilities such as hydrazine hydrate, sodium borohydride, dimethyl formamide, formaldehyde are strong, toxicity is big, experiment harmfulness is big, species, environment are all had potential menace; 3. according to requirement dispersed and particle size, protective agent commonly used has polyaniline, polyvinylpyrrolidone, octadecylamine etc., also all is environmentally harmful reagent.
Therefore explore a kind of method of dendroid platinum nano-cluster of preparation high electrocatalytic active of green; The higher value of environmental protection is not only arranged; Can also improve the utilization rate of platinum effectively, reduce cost, increase economy; Application Research for promoting fuel cell platinum group nanocatalyst is significant, simultaneously later industrialization is also had directive significance.
Summary of the invention
The object of the present invention is to provide a kind of green synthesis method of dendroid platinum nano-cluster of high electrocatalytic active.The dendroid platinum nano-cluster productive rate that this method is prepared is high, purity is high, pattern is unified, good dispersion; Have higher specific surface area, can improve electro-catalysis efficient effectively; Have the higher stable durability simultaneously concurrently; And its preparation technology is simple to operate, and controllability is strong, is beneficial to suitability for industrialized production.
The present invention proposes a kind of green synthesis method of dendroid platinum nano-cluster of high electrocatalytic active; May further comprise the steps 1., platinum presoma and triblock copolymer are scattered in the distilled water; Be made into mol ratio and be 2～50: 1 solution, the preferred 0.2-2.5mmol/L of triblock copolymer; 2., ultrasonic dispersion makes triblock copolymer and the abundant mixing of platinum presoma; 3., leave standstill and make the abundant coordination absorption of triblock copolymer and platinum presoma ion; 4., place 80～100 ℃ of water-baths to heat 2～48 hours, obtain dendroid platinum nano-cluster.
Triblock copolymer comprises four series such as Pluronic R, Pluronic F, Pluronic L, Pluronic P among the above-mentioned preparation method.
The both affected template of triblock copolymer among the above-mentioned preparation method, protective agent, also play the effect of reducing agent simultaneously, through changing 80～100 ℃ of heating-up temperatures, the rate of reduction of regulating the platinum presoma through the structure of rising temperature change molecule.Through changing 2～48 hours heat time heating times, to improve the amount of cure of nano platinum particle bunch.
Different types of platinum presoma comprises H among the above-mentioned preparation method 2PtCl 6, K 2PtCl 6, K 2PtCl 4Etc. common inorganic platinum source.
Heat in preferred 100 ℃ of water-baths among the above-mentioned preparation method.
Ultrasonic energy mixes triblock copolymer and platinum presoma among the above-mentioned preparation method.
Leave standstill among the above-mentioned preparation method and can make triblock copolymer with the abundant coordination absorption of its hydrophilic polyoxyethylene section (PEO) platinum presoma ion.
The prepared dendroid platinum nano-cluster that obtains of the present invention has higher specific surface area; Good electro catalytic activity and stable durability; The demand for development that meets fuel-cell catalyst economical and efficient property, experiment reagent is nontoxic simultaneously, embodies the advantage of green preparation.
Description of drawings:
Fig. 1 is the flow chart of the dendroid platinum nano-cluster of green synthetic high electrocatalytic active;
Fig. 2 is the TEM figure of the platinum nano-cluster that makes among the embodiment 1;
Fig. 3 is the TEM figure of the platinum nano-cluster that makes among the embodiment 2;
Fig. 4 is the TEM figure of the platinum nano-cluster that makes among the embodiment 3;
Fig. 5 is the TEM figure of the platinum nano-cluster that makes among the embodiment 4;
Fig. 6 is the TEM figure of the platinum nano-cluster that makes among the embodiment 5;
Fig. 7 is the TEM figure of the platinum nano-cluster that makes among the embodiment 6;
Fig. 8 is the TEM figure of the platinum nano-cluster that makes among the embodiment 7;
Fig. 9 is the XRD figure of the platinum nano-cluster that makes among the embodiment 1;
Figure 10 for the platinum nano-cluster that makes among the embodiment 1 at 0.5mol L -1H 2SO 4Electrochemistry cyclic voltammetry curve in the solution under the saturated atmosphere of argon gas;
Figure 11 for the platinum nano-cluster that makes among the embodiment 1 at 0.5mol L -1H 2SO 4Electrochemistry cyclic voltammetry curve in the solution under the saturated atmosphere of oxygen;
Figure 12 for the platinum nano-cluster that makes among the embodiment 1 at 0.5mol L -1H 2SO 4Electrochemistry linear scanning curve in the solution under the saturated atmosphere of oxygen;
The specific embodiment
Embodiment 1
Building-up process is referring to Fig. 1: 0.1008g Pluronic F127 is added two mouthfuls of flasks of 50ml, add 10ml distilled water, ultrasonic dispersion adds 10ml H 2PtCl 6(20mMol/L) aqueous solution, ultrasonic mixing makes Pluronic F127 and PtCl 6 2-Mol ratio be 25: 1, left standstill 1 hour.Thereafter 100 ℃ of reflux are 5 hours, obtain black precipitate.With the crystalline form of polycrystalline X-ray diffractometer (XRD) detection black precipitate, the result shows that product is the simple substance platinum (see figure 9) of face-centred cubic structure; Confirm that with atomic emission spectrum (ICP) degree of purity of production is 88.6%; With the pattern of transmission electron microscope (TEM) sign product, the result shows that products therefrom is the dendritic platinum nano-cluster of a three-dimensional tree (see figure 2).
Embodiment 2
Building-up process is referring to Fig. 1: 0.0230g Pluronic P123 is added two mouthfuls of flasks of 50ml, add 10ml distilled water, ultrasonic dispersion adds 10ml H 2PtCl 6(20mMol/L) aqueous solution, ultrasonic mixing makes Pluronic P123 and PtCl 6 2-Mol ratio be 50: 1, left standstill 1 hour, 90 ℃ of reflux are 24 hours thereafter, obtain black precipitate.With the crystalline form of polycrystalline X-ray diffractometer (XRD) detection black precipitate, the result shows that product is the simple substance platinum of face-centred cubic structure; Confirm that with atomic emission spectrum (ICP) degree of purity of production is 90.3%; With the pattern of transmission electron microscope (TEM) sign product, the result shows that products therefrom is a thorniness platinum nanometer star bunch (see figure 3).
Embodiment 3
Building-up process is referring to Fig. 1: 0.0290g Pluronic L64 is added two mouthfuls of flasks of 50ml, add 10ml distilled water, ultrasonic dispersion adds 10ml K 2PtCl 4(50mMol/L) aqueous solution, ultrasonic mixing makes Pluronic L64 and PtCl 4 2-Mol ratio be 50: 1, left standstill 1 hour, 80 ℃ of reflux are 24 hours thereafter, obtain black precipitate.With the crystalline form of polycrystalline X-ray diffractometer (XRD) detection black precipitate, the result shows that product is the simple substance platinum of face-centred cubic structure; Confirm that with atomic emission spectrum (ICP) degree of purity of production is 91.3%; With the pattern of transmission electron microscope (TEM) sign product, the result shows that products therefrom is a bunch (see figure 4) of uniting of cerioid nano platinum particle.
Embodiment 4
Building-up process is referring to Fig. 1: 0.0300g Pluronic 17R8 is added two mouthfuls of flasks of 50ml, add 10ml distilled water, ultrasonic dispersion adds 10ml K 2PtCl 6(10mMol/L) aqueous solution, ultrasonic mixing makes Pluronic 17R8 and PtCl 6 2-Mol ratio be 25: 1, left standstill 1 hour, 100 ℃ of reflux are 48 hours thereafter, obtain black precipitate.With the crystalline form of polycrystalline X-ray diffractometer (XRD) detection black precipitate, the result shows that product is the simple substance platinum of face-centred cubic structure; Confirm that with atomic emission spectrum (ICP) degree of purity of production is 89.7%; Characterize the pattern of product with transmission electron microscope (TEM), the result shows that the products therefrom occurrence of large-area reunites, the platinum nano-cluster (see figure 5) that generates intensive.
Embodiment 5
Building-up process is referring to Fig. 1: 0.0840g Pluronic F127 is added two mouthfuls of flasks of 50ml, add 10ml distilled water, ultrasonic dispersion adds 10ml H 2PtCl 6(20mMol/L) aqueous solution, ultrasonic mixing makes Pluronic F127 and PtCl 6 2-Mol ratio be 30: 1, left standstill 1 hour.Thereafter 100 ℃ of reflux are 2 hours, obtain black precipitate.With the crystalline form of polycrystalline X-ray diffractometer (XRD) detection black precipitate, the result shows that product is the simple substance platinum of face-centred cubic structure; Confirm that with atomic emission spectrum (ICP) degree of purity of production is 89.4%; With the pattern of transmission electron microscope (TEM) sign product, the result shows that products therefrom is the dendritic platinum nano-cluster of a two dimensional trees (see figure 6).
Embodiment 6
Building-up process is referring to Fig. 1: 0.6300g Pluronic F127 is added two mouthfuls of flasks of 50ml, add 10ml distilled water, ultrasonic dispersion adds 10ml K 2PtCl 4(50mMol/L) aqueous solution, ultrasonic mixing makes Pluronic F127 and PtCl 4 2-Mol ratio be 10: 1, left standstill 1 hour.Thereafter 90 ℃ of reflux are 3.5 hours, obtain black precipitate.With the crystalline form of polycrystalline X-ray diffractometer (XRD) detection black precipitate, the result shows that product is the simple substance platinum of face-centred cubic structure; Confirm that with atomic emission spectrum (ICP) degree of purity of production is 90.1%; With the pattern of transmission electron microscope (TEM) sign product, the result shows that products therefrom is monodispersed platinum nanosphere and the mixing intermediateness that tentatively shows the platinum nano-cluster of branch structure.(see figure 7).
Embodiment 7
Building-up process is referring to Fig. 1: 0.2875g Pluronic P123 is added two mouthfuls of flasks of 50ml, add 10ml distilled water, ultrasonic dispersion adds 10ml K 2PtCl 6(10mMol/L) aqueous solution, ultrasonic mixing makes Pluronic P123 and PtCl 6 2-Mol ratio be 2: 1, left standstill 1 hour, 80 ℃ of reflux are 36 hours thereafter, obtain black precipitate.With the crystalline form of polycrystalline X-ray diffractometer (XRD) detection black precipitate, the result shows that product is the simple substance platinum of face-centred cubic structure; Confirm that with atomic emission spectrum (ICP) degree of purity of production is 89.8%; With the pattern of transmission electron microscope (TEM) sign product, the result shows that products therefrom is single Pt nanoparticle (see figure 8) of disperseing.
Embodiment 7
The dendroid platinum nano-cluster eelctro-catalyst of instance 1 gained is processed working electrode, adopt traditional three-electrode system, standard hydrogen electrode is a reference electrode, and the glass carbon plate carries out electro-chemical test as auxiliary electrode, and Figure 10 has provided it at 0.5mol L -1H 2SO 4Cyclic voltammetry curve under the middle argon gas saturation conditions, sweep speed is 50mVs -1Figure 11 has provided it at 0.5mol L -1H 2SO 4Cyclic voltammetry curve under the middle oxygen-saturated conditions, sweep speed is 50mVs -1Figure 12 has provided it at 0.5mol L -1H 2SO 4Linear scan curve under the middle oxygen-saturated conditions, sweep speed is 10mVs -1, rotating speed is 1600rpm.The result shows that prepared dendroid platinum nano-cluster has higher electro-chemical activity area, is approximately 56m 2g -1, and have higher redox active.

Claims (6)

1. the green synthesis method of the dendroid platinum nano-cluster of a high electrocatalytic active is characterized in that, may further comprise the steps: 1., platinum presoma and triblock copolymer are scattered in the distilled water, be made into mol ratio and be 2～50: 1 solution; 2., ultrasonic dispersion makes triblock copolymer and the abundant mixing of platinum presoma; 3., leave standstill and make the abundant coordination absorption of triblock copolymer and platinum presoma ion; 4., place 80～100 ℃ of water-baths to heat 2～48 hours, obtain dendroid platinum nano-cluster.
2. according to the method for claim 1, it is characterized in that step is triblock copolymer substrate concentration 0.2-2.5mmol/L 1..
3. according to the method for claim 1, it is characterized in that said triblock copolymer comprises Pluronic R, Pluronic F, Pluronic L, Pluronic P.
4. according to the method for claim 1, it is characterized in that the platinum presoma is inorganic platinum source.
5. according to the method for claim 1, it is characterized in that the platinum presoma is H 2PtCl 6, K 2PtCl 6, K 2PtCl 4
6. according to the method for claim 1, it is characterized in that the preferred 100 ℃ water-baths of step in 4..
CN201110119977.1A 2011-05-10 2011-05-10 Green synthetic method for dendritic platinum nanocluster electrocatalyst Expired - Fee Related CN102773093B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201110119977.1A CN102773093B (en) 2011-05-10 2011-05-10 Green synthetic method for dendritic platinum nanocluster electrocatalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201110119977.1A CN102773093B (en) 2011-05-10 2011-05-10 Green synthetic method for dendritic platinum nanocluster electrocatalyst

Publications (2)

Publication Number Publication Date
CN102773093A true CN102773093A (en) 2012-11-14
CN102773093B CN102773093B (en) 2014-02-26

Family

ID=47118336

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201110119977.1A Expired - Fee Related CN102773093B (en) 2011-05-10 2011-05-10 Green synthetic method for dendritic platinum nanocluster electrocatalyst

Country Status (1)

Country Link
CN (1) CN102773093B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101450380A (en) * 2007-12-03 2009-06-10 国家纳米科学中心 Bimetal nano rod of branched gold core/platinum shell structure and preparation method thereof
US20110088511A1 (en) * 2010-08-28 2011-04-21 Ghanavi Jalaledin Method for producing rod-shaped and branched metallic nano-structures by polyol compounds

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101450380A (en) * 2007-12-03 2009-06-10 国家纳米科学中心 Bimetal nano rod of branched gold core/platinum shell structure and preparation method thereof
US20110088511A1 (en) * 2010-08-28 2011-04-21 Ghanavi Jalaledin Method for producing rod-shaped and branched metallic nano-structures by polyol compounds

Also Published As

Publication number Publication date
CN102773093B (en) 2014-02-26

Similar Documents

Publication Publication Date Title
Song et al. Ruthenium@ N-doped graphite carbon derived from carbon foam for efficient hydrogen evolution reaction
CN105170169B (en) A kind of nitrogen-doped graphene iron-based nano-particles reinforcement type catalyst and preparation method thereof
CN104353480B (en) Three-dimensional nitrogen-doped graphene platinoid-loaded composite electro-catalyst and preparation method thereof
CN101733094B (en) Pt-CeO2/graphene electro-catalyst and preparation method thereof
CN110479329B (en) Preparation and application of phosphorus-doped cobalt telluride nano material
CN105688958A (en) Polyhedron cobalt phosphide/graphite carbon hybrid material and preparing method and application thereof
CN107346826A (en) A kind of preparation method of the scattered oxygen reduction electro-catalyst of monatomic iron
CN109718822B (en) Method for preparing metal-carbon composite catalytic material and application thereof
CN107051559A (en) A kind of hydrogen reduction and analysis oxygen phosphatization cobalt@NPC dual-function composite catalysts and its preparation method and application
CN102088091A (en) Carbon-carrying shell type copper-platinum catalyst for fuel cell and preparation method thereof
CN109731586B (en) Preparation method and application of copper-containing metal organic framework-derived hierarchical porous copper phosphide/carbohydrate electrolysis electrocatalyst
CN103816894B (en) Doping type graphene-supported PtRu alloy nano eelctro-catalyst and preparation method thereof
CN104667953A (en) Nitrogen-doped graphdiyne as well as preparation method and application thereof
Liu et al. Self-supported cobalt oxide electrocatalysts with hierarchical chestnut burr-like nanostructure for efficient overall water splitting
CN1171671C (en) Method for prepn. of electrode catalyst with function of anti-CD and contg. platinum and ruthenium series carried on carbon nanometer tube
CN113174608B (en) Preparation method of double-doped porous cobalt phosphide nanosheet electrocatalytic material
Wang et al. Magnetic Field‐Enhanced Electrocatalytic Oxygen Evolution on a Mixed‐Valent Cobalt‐Modulated LaCoO3 Catalyst
CN111293323B (en) Porous platinum-palladium nano cubic material, preparation method thereof and application thereof in catalyzing methanol oxidation
CN110354870B (en) Preparation method and application of high-performance silver-doped cobalt sulfide oxygen evolution catalyst
CN109301269B (en) PtAgCo/C nanoflower structure catalytic material, preparation method thereof and application of catalytic material as fuel cell catalyst
CN104707601A (en) Preparation method of electrocatalyst of proton exchange membrane fuel cell
CN102794172B (en) Photosynthesis preparation method of nano palladium catalyst
CN102773093B (en) Green synthetic method for dendritic platinum nanocluster electrocatalyst
CN108963283A (en) High-dispersion loading type core-shell structure Pd@Ni/WC direct alcohol fuel cell catalyst and preparation method thereof
CN114420950B (en) ZIF-8 derived Zn 3 (VO 4 ) 2 Electrocatalytic material and preparation method and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20140226

Termination date: 20180510

CF01 Termination of patent right due to non-payment of annual fee