CN108054391A - A kind of synthetic method of dendritic Pd nanocrystal catalysts and its application - Google Patents
A kind of synthetic method of dendritic Pd nanocrystal catalysts and its application Download PDFInfo
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- CN108054391A CN108054391A CN201711311299.2A CN201711311299A CN108054391A CN 108054391 A CN108054391 A CN 108054391A CN 201711311299 A CN201711311299 A CN 201711311299A CN 108054391 A CN108054391 A CN 108054391A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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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
- 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 kind of dendritic Pd nanocrystal catalysts preparation methods, it is characterised in that：Including following preparation process:（1）Surfactant and reducing agent are added to the water together, stirred 5 ~ 15 minutes at room temperature, the mass ratio of surfactant and reducing agent is 3:1~1:3；Institute's amount of water needs surfactant and reducing agent being completely dissolved；(2) to step（1）It is separately added into metal platinum salt precursor solution in the mixed solution of gained, the concentration of metal salt precursor solution is 0.1~1mol/L, and the ratio of mixed solution and metallic precursor overall solution volume is 25:1~35:1, the Metal Palladium salt precursor liquid solution is potassium chloropalladate, chlorine palladium is sour or the sodium salt of chlorine palladium acid, is stirred at room temperature 5 ~ 15 minutes；(3) by step（2）Gained mixed solution stirs 5 ~ 20 minutes at room temperature, and when reaction 2 ~ 4 is small in three-necked flask, temperature is controlled at 70 ~ 100 DEG C；（4）By step（3）It is washed after products therefrom cooling, there is dendritic Pd nanocrystal catalysts up to a kind of after centrifugation.
Description
Technical field
The present invention relates to aminic acid fuel battery catalyst field, specifically a kind of dendritic Pd nanocrystal catalysts
Synthesis and its application.
Background technology
For fuel cell since its energy transformation ratio is high, environmental pollution is small, advantageously reduces the excessive of conventional fossil fuel
Use and preserve our planet environment, can be as the power resources of future ideality, thus is subject to the extensive concern of countries in the world scientist,
For this purpose, countries in the world have put into substantial amounts of manpower and materials and financial resources to be studied.Direct methanoic acid fuel cell in electric vehicle,
There is the prospect greatly applied in terms of mobile power supply equipment.In the catalysis to formic acid, compared to Pt metals, Pd metals have
Price is low, the strong advantage of catalytic performance, at present the preparation method of catalyst have high-temperature alloy method, gas phase reduction process, sol method,
B.nnemann methods, liquid phase reduction, intermittent microwave local reduction way, solid reaction process, cosputtering method etc..For catalyst
Research is mainly studied in terms of reducing agent, surfactant, pattern, dispersion degree, structure etc. are several, is lived so as to prepare catalysis
Property high, the good catalyst of stability.But at present morphology controllable preparation Pd nanocatalysts mainly using autoclave into
Row synthesis, usual synthesis temperature are more than 100 DEG C.Such method is unfavorable for operation and subsequent production application.
The content of the invention
The technical problem to be solved by the present invention is to：A kind of dendritic Pd nanocrystal catalysts are provided, enhance catalyst pair
The catalytic activity of formic acid.
The technical scheme is that：A kind of dendritic Pd nanocrystal catalysts preparation method, including following preparation process:
（1）Surfactant and reducing agent are added to the water together, stirred 5 ~ 15 minutes at room temperature, the matter of surfactant and reducing agent
Amount is than being 3:1~1:3；Institute's amount of water needs surfactant and reducing agent being completely dissolved；(2) to step（1）Gained
Metal platinum salt precursor solution is separately added into mixed solution, the concentration of metal salt precursor solution is 0.1~1mol/L, is mixed
Solution and the ratio of metallic precursor overall solution volume are 25:1~35:1, the Metal Palladium salt precursor liquid solution is chlorine palladium acid
The sodium salt of potassium, chlorine palladium acid or chlorine palladium acid, is stirred at room temperature 5 ~ 15 minutes；(3) by step（2）Gained mixed solution stirs at room temperature
It mixes 5 ~ 20 minutes, when reaction 2 ~ 4 is small in three-necked flask, temperature is controlled at 70 ~ 100 DEG C；（4）By step（3）Products therefrom is cold
But washed afterwards, there is dendritic Pd nanocrystal catalysts up to a kind of after centrifugation.
Step（1）The aqueous solution is ultra-pure water, and mixing time is 10 minutes, surfactant and reducing agent mass ratio
For 3.2:1.1.
The step（1）In surfactant agent be glycine or CTAC；Reducing agent is ascorbic acid.
Step（2）The metal salt precursor solution concentration is 0.1 mol/L, and Metal Palladium salt precursor liquid solution is chlorine palladium
Sour sodium.
Step（3）Described to stir 10 minutes at room temperature, when reaction 3 is small in three-necked flask, temperature is controlled at 95 DEG C.
The step（4）In be cooled to natural cooling, washing three times, centrifuges four times, both dendritic Pd is nanocrystalline
Body.
Beneficial effects of the present invention：The present invention prepares a kind of dendritic（dendritic）Pd nanocrystal catalysts, it is excellent
Gesture be it is easy to operate, it is environmental-friendly, to appointed condition require it is low, the dendritic Pd nanocatalysts of gained have good dispersion, grain
Footpath is homogeneous, the advantages that being had excellent performance to Catalyzed by Formic Acid.
The present invention studies and obtains a kind of dendritic Pd nanocrystal catalysts, preferably enhances the formic acid oxygen of catalyst
Change catalytic activity, in 0.1M HClO4The mass activity peak point current that its in+0.5MHCOOH is catalyzed formic acid is 3.3 A mg-1, than
The 0.36 A mg of business Pd black-1It is 9.1 times high；In 0.1M H2SO4Its in+0.5MHCOOH is catalyzed the mass activity of formic acid
Peak point current is 1.08 A mg-1, the 0.12 A mg than business Pd black-1It is 9.0 times high.
Description of the drawings
Fig. 1 is dendritic Pd nanocrystal catalysts, and result figure is observed with high resolution transmission electron microscope；
Fig. 2 is dendritic Pd nanocrystal catalysts, and result figure is observed with high resolution transmission electron microscope；
Fig. 3 is dendritic Pd nanocrystal catalysts and business Pd black in 0.1MHClO4It is cycled in+0.5MHCOOH solution
Volt-ampere curve figure；
Fig. 4 is dendritic Pd nanocrystal catalysts and business Pd black in 0.1MH2SO4It is cycled in+0.5MHCOOH solution
Volt-ampere curve figure；
Fig. 5 is dendritic Pd nanocrystal catalysts and business Pd black in 0.1MHClO40.1V in+0.5MHCOOH solution
Under conditions of i-t curves；
Fig. 6 is dendritic Pd nanocrystal catalysts and business Pd black in 0.1MH2SO40.1V in+0.5MHCOOH solution
Under conditions of i-t curves；
Fig. 7 observes result figure for reversed embodiment Pd branched nanocrystal catalyst high resolution transmission electron microscope；
Fig. 8 is reversed embodiment Pd branched nanocrystal catalyst in 0.5MH2SO4Cyclic voltammetric is bent in+0.5MHCOOH solution
Line chart.
Specific embodiment
Embodiment 1
（1）By surfactant and reducing agent in mass ratio 3:1 is added in aqueous solution, stirs 10 minutes；Surfactant agent
For CTAC, reducing agent is ascorbic acid；
（2）To step（1）Mixed solution（14.5mL）Middle addition platinum acid chloride solution, concentration 0.1mol/L, mixed solution
Color is yellow, is stirred 10 minutes at room temperature；
（3）By step（2）The solution of gained is transferred in three-necked flask, reacts 3h, and temperature is controlled at 95 DEG C or so；
（4）Products obtained therefrom after centrifuging and being carried out with alcoholic solution 3 washings in alcoholic solution, preferably, urge distributed and saved by dispersiveness
Change activity.
Embodiment 2
（1）By surfactant and reducing agent in mass ratio 2:1 is added in aqueous solution, stirs 15 minutes；Surfactant agent
For glycine, reducing agent is ascorbic acid；
（2）To step（1）Mixed solution（14.5mL）Middle addition platinum acid chloride solution, concentration 0.1mol/L, mixed solution
Color is yellow, is stirred 10 minutes at room temperature；
（3）By step（2）The solution of gained is transferred in three-necked flask, reacts 3h, and temperature is controlled at 95 DEG C or so；
（4）Products obtained therefrom after centrifuging and being carried out with alcoholic solution 3 washings in alcoholic solution, preferably, urge distributed and saved by dispersiveness
Change activity preferably.
Comparative example 1
（1）By Na2PdCl4, CTAB, Ni(ac)2Added in ascorbic acid in 20mL water, make its concentration be respectively 2.5 ×
10−4 M, 1.5 × 10−2 M, 1.0 × 10−5 M, and 2.5 × 10−3 M。
（2）Reactor is placed on stand and heat in 30 DEG C of water-baths 2 it is small when.
（3）Make placement temperature be increased to 60 DEG C and heat 1.5 it is small when.
（4）Products obtained therefrom is through centrifuging and repeatedly being washed with the aqueous solution of alcohol.
（5）Sample is dried in 60 DEG C of vacuum environments.
（6）In ozone environment, CTAB is removed within several hours with ultraviolet light sample.
By that can be found compared with comparative example 1, comparative example compares this experiment and has used expensive Ni（ac）2Increase
Add cost, and operating procedure is more, late-run sample processing method is complicated.
Fig. 1 is the projection electron microscope that catalyst obtained by embodiment carries out, it can be seen that dendritic Pd crystalline nanometrics catalysis
Agent size is more homogeneous.
Fig. 2 is the high-resolution projection electron microscope that catalyst obtained by embodiment carries out, it can be seen that dendritic Pd crystal
Nanocatalyst surface topography is homogeneous and is made of strip.
The dendritic catalyst of Fig. 3 Pd obtained by embodiment and business use Pd black in 0.1MHClO4+ 0.5MHCOOH is molten
The cyclic voltammetry curve figure of formic acid is catalyzed in liquid, it can be seen that the peak point current highest of wherein dendritic Pd is 3.3A mg-1To be same
Etc. commercialization Pd is black under test conditions 9.1 times.
The dendritic catalyst of Fig. 4 Pd obtained by embodiment and business use Pd black in 0.1MH2SO4+ 0.5MHCOOH is molten
The cyclic voltammetry curve figure of formic acid is catalyzed in liquid, it can be seen that the peak point current highest of wherein dendritic Pd is 1.1A mg-1To be same
Etc. commercialization Pd is black under test conditions 9 times.
Fig. 5 is that catalyst obtained by embodiment and commercial Pd are black in 0.1MHClO4The item of 0.1V in+0.5MHCOOH solution
I-t curves, testing time 3600s, the results showed that the Pd crystal catalysts of dendritic morphology are in the peak point current of 3600s are surveyed under part
More black than commercial Pd always high, stability is got well than commercial Pd is black.
Fig. 6 is that catalyst obtained by embodiment and commercial Pd are black in 0.1MH2SO4The item of 0.1V in+0.5MHCOOH solution
I-t curves, testing time 3600s, the results showed that the Pd crystal catalysts of dendritic morphology are in the peak point current of 3600s are surveyed under part
More black than commercial Pd always high, stability is got well than commercial Pd is black.
Fig. 7 is the high-resolution projection electron microscope that the Pd DN catalyst obtained by reversed embodiment carries out, it can be seen that
Its pattern size is inhomogenous.
Fig. 8（b）It is the dendritic catalyst of Pd obtained by comparative example in 0.5MH2SO4Mass activity in+0.5MHCOOH
For 0.178mA/mg, far below the mass activity of dendritic Pd in the application patent（1.1A /mg）.
Claims (6)
1. a kind of dendritic Pd nanocrystal catalysts preparation method, it is characterised in that：Including following preparation process:（1）By surface
Activating agent and reducing agent are added to the water together, stir 5 ~ 15 minutes at room temperature, and the mass ratio of surfactant and reducing agent is 3:1
~1:3；Institute's amount of water needs surfactant and reducing agent being completely dissolved；(2) to step（1）The mixed solution of gained
In be separately added into metal platinum salt precursor solution, the concentration of metal salt precursor solution is 0.1~1mol/L, mixed solution and gold
The ratio for belonging to precursor solution total volume is 25:1~35:1, the Metal Palladium salt precursor liquid solution is potassium chloropalladate, chlorine palladium acid
Or the sodium salt of chlorine palladium acid, it is stirred at room temperature 5 ~ 15 minutes；(3) by step（2）Gained mixed solution stirs 5 ~ 20 points at room temperature
Clock, when reaction 2 ~ 4 is small in three-necked flask, temperature is controlled at 70 ~ 100 DEG C；（4）By step（3）It is carried out after products therefrom cooling
Washing has dendritic Pd nanocrystal catalysts after centrifugation up to a kind of.
2. a kind of dendritic Pd nanocrystal catalysts preparation method according to claim 1, it is characterised in that：Step（1）
The aqueous solution is ultra-pure water, and mixing time is 10 minutes, and surfactant is 3.2 with reducing agent mass ratio:1.1.
3. a kind of dendritic Pd nanocrystal catalysts preparation method according to claim 1, it is characterised in that：The step
Suddenly（1）In surfactant agent be glycine or CTAC；Reducing agent is ascorbic acid.
4. a kind of dendritic Pd nanocrystal catalysts preparation method according to claim 1, it is characterised in that：Step（2）
The metal salt precursor solution concentration is 0.1 mol/L, and Metal Palladium salt precursor liquid solution is chlorine palladium acid sodium.
5. a kind of dendritic Pd nanocrystal catalysts preparation method according to claim 1, it is characterised in that：Step（3）
Described to stir 10 minutes at room temperature, when reaction 3 is small in three-necked flask, temperature is controlled at 95 DEG C.
6. a kind of dendritic Pd nanocrystal catalysts preparation method according to claim 1, it is characterised in that：The step
Suddenly（4）In be cooled to natural cooling, washing three times, centrifuges four times, both dendritic Pd nanocrystals.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108682876A (en) * | 2018-06-04 | 2018-10-19 | 黑龙江省科学院石油化学研究院 | A kind of high activity has the cube nano Pd catalyst and preparation method thereof of meso-hole structure |
| CN108963273A (en) * | 2018-06-27 | 2018-12-07 | 华南理工大学 | A kind of branch shape platinum elctro-catalyst and the preparation method and application thereof |
| CN109449450A (en) * | 2018-11-27 | 2019-03-08 | 浙江工业大学 | A kind of palladium ruthenium nanometer thorn assembling body catalyst and preparation method thereof |
| CN109732100A (en) * | 2019-03-11 | 2019-05-10 | 昆明理工大学 | A kind of preparation method of the dendritic Pt nanoparticle of small size |
| CN110010914A (en) * | 2019-04-08 | 2019-07-12 | 贵州大学 | A kind of one-dimensional PtCuCo alloy nano chain catalyst and synthetic method suitable for methanol fuel cell under high temperature |
| CN111318721A (en) * | 2020-03-19 | 2020-06-23 | 四川省疾病预防控制中心 | Preparation method of platinum nano-chain |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775638A (en) * | 2010-03-24 | 2010-07-14 | 中国科学院长春应用化学研究所 | Preparation method of palladium nano crystal |
| JP2011026665A (en) * | 2009-07-27 | 2011-02-10 | National Institute For Materials Science | Metal nanoparticle having dendritic portion and method for producing the same |
| CN105332050A (en) * | 2015-11-30 | 2016-02-17 | 中国科学技术大学 | Palladium nanocrystals and synthesis method thereof |
| CN105958087A (en) * | 2016-06-08 | 2016-09-21 | 贵州大学 | General preparation method for flower-like porous platinum-based nano-catalyst |
-
2017
- 2017-12-11 CN CN201711311299.2A patent/CN108054391B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011026665A (en) * | 2009-07-27 | 2011-02-10 | National Institute For Materials Science | Metal nanoparticle having dendritic portion and method for producing the same |
| CN101775638A (en) * | 2010-03-24 | 2010-07-14 | 中国科学院长春应用化学研究所 | Preparation method of palladium nano crystal |
| CN105332050A (en) * | 2015-11-30 | 2016-02-17 | 中国科学技术大学 | Palladium nanocrystals and synthesis method thereof |
| CN105958087A (en) * | 2016-06-08 | 2016-09-21 | 贵州大学 | General preparation method for flower-like porous platinum-based nano-catalyst |
Non-Patent Citations (1)
| Title |
|---|
| YOUNG WOOK LEE: "Shaping Pd nanocatalysts through the control of reaction sequence", 《CHEM.COMMUN》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108682876A (en) * | 2018-06-04 | 2018-10-19 | 黑龙江省科学院石油化学研究院 | A kind of high activity has the cube nano Pd catalyst and preparation method thereof of meso-hole structure |
| CN108963273A (en) * | 2018-06-27 | 2018-12-07 | 华南理工大学 | A kind of branch shape platinum elctro-catalyst and the preparation method and application thereof |
| CN109449450A (en) * | 2018-11-27 | 2019-03-08 | 浙江工业大学 | A kind of palladium ruthenium nanometer thorn assembling body catalyst and preparation method thereof |
| CN109732100A (en) * | 2019-03-11 | 2019-05-10 | 昆明理工大学 | A kind of preparation method of the dendritic Pt nanoparticle of small size |
| CN110010914A (en) * | 2019-04-08 | 2019-07-12 | 贵州大学 | A kind of one-dimensional PtCuCo alloy nano chain catalyst and synthetic method suitable for methanol fuel cell under high temperature |
| CN111318721A (en) * | 2020-03-19 | 2020-06-23 | 四川省疾病预防控制中心 | Preparation method of platinum nano-chain |
| CN111318721B (en) * | 2020-03-19 | 2022-04-15 | 四川省疾病预防控制中心 | Preparation method of platinum nano-chain |
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