CN109833835A - A kind of preparation method of the hollow platinum palladium nano-crystal body of inner concave shape, the hollow platinum palladium nano-crystal body of inner concave shape and its application - Google Patents
A kind of preparation method of the hollow platinum palladium nano-crystal body of inner concave shape, the hollow platinum palladium nano-crystal body of inner concave shape and its application Download PDFInfo
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Abstract
The invention belongs to function nano field of material technology.The invention discloses a kind of preparation methods of the hollow platinum palladium nano-crystal body of inner concave shape, the synthetic method removes palladium core to obtain the hollow platinum palladium nano-crystal body of inner concave shape the following steps are included: using indent palladium nano-crystal body as template uniform deposition platinum nanoshells by selective chemical etching；The invention also discloses a kind of hollow platinum palladium nano-crystal body of inner concave shape and its applications.Method provided by the invention has successfully obtained the hollow platinum palladium nano-crystal body of inner concave shape, and synthesis technology is simple, and synthesis condition is mild, is suitble to prepare with scale.The hollow platinum palladium nano-crystal body of the inner concave shape that the present invention obtains is the hollow platinum palladium nano-crystal body that outermost layer is high miller index surface, which can also be greatly improved the latent active on platinum surface while improving pt utilization.Catalyst and synthesis technology prepared by the present invention are able to satisfy the demand of fuel battery cathod catalyst, have help to promotion fuel cell industrialization.
Description
Technical field
The present invention relates to function nano field of material technology, more particularly, to a kind of hollow platinum palladium nano-crystal body of inner concave shape
The hollow platinum palladium nano-crystal body of preparation method, inner concave shape and its application.
Background technique
Why so flourishing modern chemical industry industry is, is able to continuously and produces the chemical products that can meet people's demand and be
Because catalyst is widely used in modern chemical industry industry.Typically, the effect of catalyst can be generalized into three aspects:
The activation energy for reducing reaction, becomes possible for the chemical reaction that can not thermodynamically can be carried out；The rate of reaction is improved, is improved anti-
The dynamics answered reduces the purpose of energy consumption of reaction to reach reduction reaction temperature；The reaction energy barrier for reducing target product, mentions
The selectivity of high target product.In general, catalyst is from catalysis reaction, there is no variations for quality and structure, wherein
Active site is the atom at catalyst surface and interface, and surface and interface structure can influence absorption and the activation power of substrate molecule
It learns, and then influences the catalytic activity of catalyst entirety.Catalyst is widely used in chemical industry, such as petrochemical industry,
Fuel cell, vehicle maintenance service etc..
Fuel cell is a kind of novel Energy Conversion Technology, its working principle is that converting chemical energy into electric energy, generally
For in anode oxidation reaction occurs, such as hydrogen or methanol, formic acid are oxidized to carbon dioxide and water, and oxygen occurs for cathode also
Original reaction generates water.At this stage, a large amount of burnings of fossil energy bring environmental pollution very serious, and greenhouse effects are increasingly
Seriously；On the other hand, fossil energy also faces exhausted danger, how to maintain the balance of energy supply, and to the side such as environmental protection
The double requirements in face find the important directions for cleaning that the sustainable energy is researcher at this stage.Fuel cell technology is complete
Full up foot at this stage shows the requirement of clean energy resource with the appearance of the hydrogen cell automobile of Japanese first commercialization
Fuel cell functionization has stepped essential step, also implies that fuel cell technology is with a wide range of applications.
The key technology bottleneck of fuel cell technology is that the oxygen reduction reaction of cathode is the slower reaction of a dynamics, because
This improves the output power of fuel cell, cathode is widely used noble metal platinum and makees catalyst to improve reaction rate.Due to platinum
Content in the earth's crust is lower, the higher cost of catalyst, therefore hinders the commercialization of fuel cell.Although alkaline at this stage
Cathodic oxygen reduction catalyst in medium makes great progress, however the commercialization platinum catalyst in acid medium can't
Substitution.Therefore, how to realize that it is a significant challenge that the activity of platinum catalyst is improved while reducing platinum catalyst dosage.
For nanocatalyst, high miller index surface is generally acknowledged that with higher catalytic activity, this is mainly due to
There are a large amount of step sites for high miller index surface, while hollow structure can significantly improve the number of active sites of catalyst, reduce
The dosage of catalyst also helps substrate molecule from inside and outside two sides and touches catalyst surface, therefore is a kind of catalysis of optimization
Agent design.However hollow structure and high miller index surface how are realized simultaneously there are no mature techniques at this stage.
Summary of the invention
To solve the above problems, the present invention provides a kind of preparation of magnanimity while there is high miller index surface and hollow structure platinum
The synthetic method of palladium nano-crystal body, this method have the characteristics that reaction condition is mild, yield is high and purity is good；
The present invention also provides a kind of hollow platinum palladium nano-crystal bodies of inner concave shape prepared by the above method；
The present invention also provides a kind of hollow platinum palladium nano-crystal body applications of inner concave shape.
To achieve the above object, technical solution provided by the invention is as follows:
A kind of preparation method of the hollow platinum palladium nano-crystal body of inner concave shape, comprising the following steps:
A) it will be made after palladium source compound and surfactant, reducing agent, the first solvent and surface capping agents hybrid reaction and washing
Obtain palladium nano-crystal body；
B) it disperses palladium nano-crystal body in the first solvent, and palladium source compound, surfactant, reducing agent and surface packet is added
Indent palladium nano-crystal body is made after covering agent hybrid reaction；
C) it disperses indent palladium nano-crystal body in the second solvent, and surfactant, platinum source compound, reducing agent mixing is added
Inner concave shape palladium platinum core-shell nanocrystals are made after reacting and washing；
D) the hollow platinum palladium nano-crystal body of inner concave shape is made through chemical etching in inner concave shape palladium platinum core-shell nanocrystals.
Preferably, step d) is specifically, disperse inner concave shape palladium platinum core-shell nanocrystals in third solvent, addition table
Insulation reaction after face activating agent, etching agent mixing, the then hollow platinum palladium nano-crystal body of washed obtained inner concave shape.
Preferably, the preparation method of the hollow platinum palladium nano-crystal body of inner concave shape specifically includes the following steps:
A) after palladium source compound being mixed with surfactant, reducing agent, the first solvent and surface capping agents at 10~180 DEG C
Palladium nano-crystal body is made in reaction 100~180 minutes after being then centrifuged for, washing；
B) it disperses palladium nano-crystal body in the first solvent, and palladium source compound, surfactant, reducing agent and surface packet is added
100~180 minutes obtained indent palladium nano-crystal bodies are reacted at 10~180 DEG C after covering agent mixing；
C) it disperses indent palladium nano-crystal body in the second solvent, and surfactant, platinum source compound, reducing agent mixing is added
It is reacted 5~15 hours at 30~200 DEG C afterwards, inner concave shape palladium platinum core-shell nanocrystals is made after being then centrifuged for, washing；
D) disperse inner concave shape palladium platinum core-shell nanocrystals in third solvent, be added surfactant, etching agent mixing after
It is reacted 100~180 minutes at 10~180 DEG C, is then centrifuged, washs the hollow platinum palladium nano-crystal body of obtained inner concave shape.
Preferably, step a), reaction temperature b) and d) are 30~120 DEG C.
Preferably, step a), reaction temperature b) and d) are 60~120 DEG C.
Preferably, step a), reaction temperature b) and d) are 80 DEG C.
Preferably, the reaction temperature of step c) is 30~180 DEG C.
Preferably, the reaction temperature of step c) is 80~180 DEG C.
Preferably, the reaction temperature of step c) is 120~180 DEG C.
Preferably, the reaction temperature of step c) is 160 DEG C.
Preferably, step a), reaction time b) and d) are 120~180 minutes.
Preferably, step a), reaction time b) and d) are 160~180 minutes.
Preferably, step a), reaction time b) and d) are 180 minutes.
Preferably, the reaction time of step c) is 8~12 hours.
Preferably, the reaction time of step c) is 10~12 hours.
Preferably, the reaction time of step c) is 12 hours.
Preferably, palladium source compound is the compound containing chlorine Asia palladium acid group, platinum source compound is containing chloroplatinic acid root
Compound.
Preferably, palladium source compound is one of potassium chloropalladite, sodium chloropalladite, ammonium chloropalladite, platinum source
Conjunction object is one of potassium chloroplatinate, platinic sodium chloride, chloroplatinic acid.
Preferably, surfactant is polyvinylpyrrolidone.
Preferably, surfactant is the polyvinylpyrrolidone that molecular weight is 30000.
Preferably, surface capping agents are at least one of potassium bromide or aminated compounds.
Preferably, reducing agent is ascorbic acid and its salt or at least one of citric acid and its salt.
Preferably, the first solvent, the second solvent and third solvent are respectively water, n,N-Dimethylformamide, ethylene glycol
Or at least one of methanol.
Preferably, the first solvent and third solvent are water, the second solvent is n,N-Dimethylformamide.
Preferably, etching agent is to contain ferric iron compound.
Preferably, being one of ferric trichloride, ferric sulfate, ferric nitrate or ferric acetate containing ferric iron compound.
Preferably, being ferric trichloride containing ferric iron compound.
Preferably, in step a) palladium source compound, surfactant, reducing agent, the first solvent, surface capping agents weight
Amount is than being 1:(1~20): (1~5): (150~500): (1~10).
Preferably, in step a) palladium source compound, surfactant, reducing agent, the first solvent, surface capping agents weight
Amount is than being 1:2:1:200:5.
Preferably, palladium nano-crystal body, the first solvent, palladium source compound, surfactant, reducing agent, table in step b)
The weight ratio of face covering is (1~5): (150~500): 1:(1~20): (1~5): (1~10).
Preferably, palladium nano-crystal body, the first solvent, palladium source compound, surfactant, reducing agent, table in step b)
The weight ratio of face covering is 2:200:1:2:1:5.
Preferably, indent palladium nano-crystal body, the second solvent, surfactant, platinum source compound, reducing agent in step c)
Weight ratio be (1~5): (150~500): (100~500): 1:(1~5).
Preferably, indent palladium nano-crystal body, the second solvent, surfactant, platinum source compound, reducing agent in step c)
Weight ratio be 1:200:100:1:1.
Preferably, inner concave shape palladium platinum core-shell nanocrystals, surfactant, etching agent, third solvent weight in step d)
Measuring ratio is
1:(30~500): (30~100): (150~500).
Preferably, inner concave shape palladium platinum core-shell nanocrystals, surfactant, etching agent, third solvent weight in step d)
Amount is than being 1:70:70:200.
Palladium source compound of the present invention is preferably the compound containing chlorine Asia palladium acid group, the change containing chlorine Asia palladium acid group
The electrode potential for closing object Pd ion is lower, it is easier to restore；Surface capping agents of the present invention are potassium bromide, aminated compounds
One or both of, potassium bromide advantageously forms cube structure in { 100 } Preferential adsorption of palladium nano-crystal；Amine chemical combination
Object is complexed during depositing platinum with platinum ion, reduces the rate of reduction of platinum, advantageously forms the platinum layer of more shell layer,
Surfactant is preferably polyvinylpyrrolidone, and the molecular weight of polyvinylpyrrolidone is preferably 30,000.Wherein polyethylene
Pyrrolidones plays the role of coated particle, conducive to dispersion.
A kind of hollow platinum palladium nano-crystal body of inner concave shape, is made by the preparation method of the hollow platinum palladium nano-crystal body of inner concave shape.
A kind of application of the hollow platinum palladium nano-crystal body of inner concave shape, using the hollow platinum-nickel alloys of inner concave shape as fuel battery negative pole
Catalyst application in oxygen reduction reaction, water-splitting reaction, acid oxygen reduction reaction or small organic molecule hydrogenation reaction.
Therefore, the invention has the following advantages:
(1) present invention is able to achieve the synthesis of the hollow platinum palladium nano-crystal body of inner concave shape, can expose high miller index surface.Moreover, this hair
The simple process of bright offer, reaction condition is mild, is able to achieve the large-scale production of catalyst；
(2) the hollow platinum palladium nano-crystal body of inner concave shape obtained through the invention, surface is concave inward structure, has high index brilliant
Face, its catalytic activity is higher for low index crystal plane；
(3) the hollow platinum palladium nano-crystal body of inner concave shape obtained through the invention, is hollow structure, hollow structure can more expose
Active site greatly reduces the dosage of platinum, while hollow structure also helps substrate molecule and touches catalysis from inside and outside two sides
Agent surface is conducive to improve catalytic activity；
(4) the hollow platinum palladium nano-crystal body of inner concave shape obtained through the invention, is platinum-nickel alloys structure, a small amount of palladium there are energy
Regulate and control the electronic structure of platinum；
(5) the hollow platinum palladium nano-crystal physical efficiency of inner concave shape obtained meets the requirement of catalysis aspect extensively through the invention, for example, firing
Expect the Cathodic oxygen reduction of battery, water-splitting reaction, small organic molecule hydrogenation reaction etc., the hollow platinum of the inner concave shape that we obtain
Palladium nano-crystal body shows higher catalytic activity in acid oxygen reduction reaction.
Detailed description of the invention
Fig. 1 is the transmission electron microscope photo of the indent palladium nano-crystal body obtained in 4 step b) of the embodiment of the present invention, mark
Ruler is 100 nanometers；
Fig. 2 is that the transmission electron microscope of the inner concave shape palladium platinum core-shell nanocrystals obtained in 4 step c) of the embodiment of the present invention shines
Piece, scale are 100 nanometers；
Fig. 3 is the transmission electron microscopy of the hollow palladium platinum core-shell nanocrystals of inner concave shape obtained in 4 step d) of the embodiment of the present invention
Mirror photo, scale are 100 nanometers；
Fig. 4 is the angle of elevation annular dark field scanning of the hollow platinum palladium nano-crystal body of inner concave shape obtained in 4 step d) of the embodiment of the present invention
Transmission electron microscope photo, scale are 100 nanometers；
Fig. 5 is the electrochemistry cyclic voltammetry curve of the hollow platinum palladium nano-crystal body catalyst of inner concave shape made from the embodiment of the present invention 4；
Fig. 6 is the redox curve of the hollow platinum palladium nano-crystal body catalyst of inner concave shape made from the embodiment of the present invention 4.
Specific embodiment
Further description of the technical solution of the present invention With reference to embodiment.
Obviously, the described embodiments are merely a part of the embodiments of the present invention, instead of all the embodiments.Based on this
Embodiment in invention, all other reality obtained by those of ordinary skill in the art without making creative efforts
Example is applied, shall fall within the protection scope of the present invention.
In the present invention, if not refering in particular to, all equipment and raw material is commercially available or the industry is common,
Method in following embodiments is unless otherwise instructed conventional method in that art.
Embodiment 1
A kind of preparation method of the hollow platinum palladium nano-crystal body of inner concave shape specifically includes the following steps:
A) it is reacted at 180 DEG C after mixing palladium source compound with surfactant, reducing agent, the first solvent and surface capping agents
100 minutes, palladium nano-crystal body is made after being then centrifuged for, washing；Palladium source compound, surfactant, reducing agent, the first solvent,
The weight ratio of surface capping agents is 1:1:1:150:1；
B) it disperses palladium nano-crystal body in the first solvent, and palladium source compound, surfactant, reducing agent and surface packet is added
100 minutes obtained indent palladium nano-crystal bodies are reacted at 180 DEG C after covering agent mixing；Palladium nano-crystal body, the first solvent, palladium source chemical combination
Object, surfactant, reducing agent, surface capping agents weight ratio be 1:150:1:1:1:1；
C) it disperses indent palladium nano-crystal body in the second solvent, and surfactant, platinum source compound, reducing agent mixing is added
It is reacted 5 hours at 200 DEG C afterwards, inner concave shape palladium platinum core-shell nanocrystals is made after being then centrifuged for, washing；Indent palladium nano-crystal body,
Second solvent, surfactant, platinum source compound, reducing agent weight ratio be 1:150:100:1:1；
D) disperse inner concave shape palladium platinum core-shell nanocrystals in third solvent, be added surfactant, etching agent mixing after
It is reacted 100 minutes at 180 DEG C, is then centrifuged, washs the hollow platinum palladium nano-crystal body of obtained inner concave shape；Inner concave shape palladium platinum nucleocapsid is received
Meter Jing Ti, surfactant, etching agent, third weight of solvent ratio are 1:30:30:150.
Wherein, palladium source compound is potassium chloropalladite, and platinum source compound is potassium chloroplatinate；Surfactant is that molecular weight is
30000 polyvinylpyrrolidone；Surface capping agents are potassium bromide；Reducing agent is ascorbic acid；First solvent and third solvent
For water, the second solvent is n,N-Dimethylformamide；Etching agent is ferric trichloride.
A kind of hollow platinum palladium nano-crystal body of inner concave shape, by the preparation method system of the hollow platinum palladium nano-crystal body of above-mentioned inner concave shape
?.
Embodiment 2
A kind of preparation method of the hollow platinum palladium nano-crystal body of inner concave shape specifically includes the following steps:
A) it is reacted at 30 DEG C after mixing palladium source compound with surfactant, reducing agent, the first solvent and surface capping agents
180 minutes, palladium nano-crystal body is made after being then centrifuged for, washing；Palladium source compound, surfactant, reducing agent, the first solvent,
The weight ratio of surface capping agents is 1:5:2:200:3；
B) it disperses palladium nano-crystal body in the first solvent, and palladium source compound, surfactant, reducing agent and surface packet is added
180 minutes obtained indent palladium nano-crystal bodies are reacted at 30 DEG C after covering agent mixing；Palladium nano-crystal body, the first solvent, palladium source chemical combination
Object, surfactant, reducing agent, surface capping agents weight ratio be 2:200:1:5:2:3；
C) it disperses indent palladium nano-crystal body in the second solvent, and surfactant, platinum source compound, reducing agent mixing is added
It is reacted 12 hours at 80 DEG C afterwards, inner concave shape palladium platinum core-shell nanocrystals is made after being then centrifuged for, washing；Indent palladium nano-crystal body,
Second solvent, surfactant, platinum source compound, reducing agent weight ratio be 2:200:150:1:2；
D) disperse inner concave shape palladium platinum core-shell nanocrystals in third solvent, be added surfactant, etching agent mixing after
It is reacted 180 minutes at 30 DEG C, is then centrifuged, washs the hollow platinum palladium nano-crystal body of obtained inner concave shape；Inner concave shape palladium platinum nucleocapsid is received
Meter Jing Ti, surfactant, etching agent, third weight of solvent ratio are 1:80:80:200.
Wherein, palladium source compound is sodium chloropalladite, and platinum source compound is platinic sodium chloride；Surfactant is that molecular weight is
30000 polyvinylpyrrolidone；Surface capping agents are methylamine；Reducing agent is sodium ascorbate；First solvent and third solvent
For methanol, the second solvent is n,N-Dimethylformamide；Etching agent is ferric sulfate.
A kind of hollow platinum palladium nano-crystal body of inner concave shape, by the preparation method system of the hollow platinum palladium nano-crystal body of above-mentioned inner concave shape
?.
Embodiment 3
A kind of preparation method of the hollow platinum palladium nano-crystal body of inner concave shape specifically includes the following steps:
A) it is reacted at 60 DEG C after mixing palladium source compound with surfactant, reducing agent, the first solvent and surface capping agents
160 minutes, palladium nano-crystal body is made after being then centrifuged for, washing；Palladium source compound, surfactant, reducing agent, the first solvent,
The weight ratio of surface capping agents is 1:7:2:250:2；
B) it disperses palladium nano-crystal body in the first solvent, and palladium source compound, surfactant, reducing agent and surface packet is added
160 minutes obtained indent palladium nano-crystal bodies are reacted at 60 DEG C after covering agent mixing；Palladium nano-crystal body, the first solvent, palladium source chemical combination
Object, surfactant, reducing agent, surface capping agents weight ratio be 2.5:250:1:8:2.5:4；
C) it disperses indent palladium nano-crystal body in the second solvent, and surfactant, platinum source compound, reducing agent mixing is added
It is reacted 10 hours at 120 DEG C afterwards, inner concave shape palladium platinum core-shell nanocrystals is made after being then centrifuged for, washing；Indent palladium nano-crystal body,
Second solvent, surfactant, platinum source compound, reducing agent weight ratio be 2.5:300:250:1:3；
D) disperse inner concave shape palladium platinum core-shell nanocrystals in third solvent, be added surfactant, etching agent mixing after
It is reacted 160 minutes at 60 DEG C, is then centrifuged, washs the hollow platinum palladium nano-crystal body of obtained inner concave shape；Inner concave shape palladium platinum nucleocapsid is received
Meter Jing Ti, surfactant, etching agent, third weight of solvent ratio are 1:100:100:250.
Wherein, palladium source compound is potassium chloropalladite, and platinum source compound is chloroplatinic acid；Surfactant is that molecular weight is
30000 polyvinylpyrrolidone；Surface capping agents are potassium bromide；Reducing agent is sodium citrate；First solvent and third solvent
For water, the second solvent is ethylene glycol；Etching agent is ferric trichloride.
A kind of hollow platinum palladium nano-crystal body of inner concave shape, by the preparation method system of the hollow platinum palladium nano-crystal body of above-mentioned inner concave shape
?.
Embodiment 4
A kind of preparation method of the hollow platinum palladium nano-crystal body of inner concave shape specifically includes the following steps:
A) it is reacted at 80 DEG C after mixing palladium source compound with surfactant, reducing agent, the first solvent and surface capping agents
180 minutes, palladium nano-crystal body is made after being then centrifuged for, washing；Palladium source compound, surfactant, reducing agent, the first solvent,
The weight ratio of surface capping agents is 1:2:1:300:5；
B) it disperses palladium nano-crystal body in the first solvent, and palladium source compound, surfactant, reducing agent and surface packet is added
180 minutes obtained indent palladium nano-crystal bodies are reacted at 80 DEG C after covering agent mixing；Palladium nano-crystal body, the first solvent, palladium source chemical combination
Object, surfactant, reducing agent, surface capping agents weight ratio be 2:200:1:2:1:5；
C) it disperses indent palladium nano-crystal body in the second solvent, and surfactant, platinum source compound, reducing agent mixing is added
It is reacted 10 hours at 160 DEG C afterwards, inner concave shape palladium platinum core-shell nanocrystals is made after being then centrifuged for, washing；Indent palladium nano-crystal body,
Second solvent, surfactant, platinum source compound, reducing agent weight ratio be 1:200:100:1:1；
D) disperse inner concave shape palladium platinum core-shell nanocrystals in third solvent, be added surfactant, etching agent mixing after
It is reacted 180 minutes at 80 DEG C, is then centrifuged, washs the hollow platinum palladium nano-crystal body of obtained inner concave shape；Inner concave shape palladium platinum nucleocapsid is received
Meter Jing Ti, surfactant, etching agent, third weight of solvent ratio are 1:70:70:200.
Wherein, palladium source compound is potassium chloropalladite, and platinum source compound is chloroplatinic acid；Surfactant is that molecular weight is
30000 polyvinylpyrrolidone；Surface capping agents are potassium bromide；Reducing agent is ascorbic acid；First solvent and third solvent
For water, the second solvent is n,N-Dimethylformamide；Etching agent is ferric trichloride.
A kind of hollow platinum palladium nano-crystal body of inner concave shape, by the preparation method system of the hollow platinum palladium nano-crystal body of above-mentioned inner concave shape
?.
Embodiment 5
A kind of preparation method of the hollow platinum palladium nano-crystal body of inner concave shape specifically includes the following steps:
A) it is reacted at 120 DEG C after mixing palladium source compound with surfactant, reducing agent, the first solvent and surface capping agents
100 minutes, palladium nano-crystal body is made after being then centrifuged for, washing；Palladium source compound, surfactant, reducing agent, the first solvent,
The weight ratio of surface capping agents is 1:15:4:400:7；
B) it disperses palladium nano-crystal body in the first solvent, and palladium source compound, surfactant, reducing agent and surface packet is added
100 minutes obtained indent palladium nano-crystal bodies are reacted at 120 DEG C after covering agent mixing；Palladium nano-crystal body, the first solvent, palladium source chemical combination
Object, surfactant, reducing agent, surface capping agents weight ratio be 4:400:1:15:4:7；
C) it disperses indent palladium nano-crystal body in the second solvent, and surfactant, platinum source compound, reducing agent mixing is added
It is reacted 8 hours at 180 DEG C afterwards, inner concave shape palladium platinum core-shell nanocrystals is made after being then centrifuged for, washing；Indent palladium nano-crystal body,
Second solvent, surfactant, platinum source compound, reducing agent weight ratio be 4:450:400:1:4；
D) disperse inner concave shape palladium platinum core-shell nanocrystals in third solvent, be added surfactant, etching agent mixing after
It is reacted 100 minutes at 120 DEG C, is then centrifuged, washs the hollow platinum palladium nano-crystal body of obtained inner concave shape；Inner concave shape palladium platinum nucleocapsid is received
Meter Jing Ti, surfactant, etching agent, third weight of solvent ratio are 1:300:40:400.
Wherein, palladium source compound is ammonium chloropalladite, and platinum source compound is potassium chloroplatinate；Surfactant is that molecular weight is
30000 polyvinylpyrrolidone；Surface capping agents are potassium bromide；Reducing agent is citric acid；First solvent and third solvent are
Water, the second solvent are n,N-Dimethylformamide；Etching agent is ferric sulfate.
A kind of hollow platinum palladium nano-crystal body of inner concave shape, by the preparation method system of the hollow platinum palladium nano-crystal body of above-mentioned inner concave shape
?.
Embodiment 6
A kind of preparation method of the hollow platinum palladium nano-crystal body of inner concave shape specifically includes the following steps:
A) it is reacted at 180 DEG C after mixing palladium source compound with surfactant, reducing agent, the first solvent and surface capping agents
100 minutes, palladium nano-crystal body is made after being then centrifuged for, washing；Palladium source compound, surfactant, reducing agent, the first solvent,
The weight ratio of surface capping agents is 1:20:5:500:10；
B) it disperses palladium nano-crystal body in the first solvent, and palladium source compound, surfactant, reducing agent and surface packet is added
100 minutes obtained indent palladium nano-crystal bodies are reacted at 180 DEG C after covering agent mixing；Palladium nano-crystal body, the first solvent, palladium source chemical combination
Object, surfactant, reducing agent, surface capping agents weight ratio be 5:500:1:20:5:10；
C) it disperses indent palladium nano-crystal body in the second solvent, and surfactant, platinum source compound, reducing agent mixing is added
It is reacted 5 hours at 200 DEG C afterwards, inner concave shape palladium platinum core-shell nanocrystals is made after being then centrifuged for, washing；Indent palladium nano-crystal body,
Second solvent, surfactant, platinum source compound, reducing agent weight ratio be 5:500:500:1:5；
D) disperse inner concave shape palladium platinum core-shell nanocrystals in third solvent, be added surfactant, etching agent mixing after
It is reacted 100 minutes at 180 DEG C, is then centrifuged, washs the hollow platinum palladium nano-crystal body of obtained inner concave shape；Inner concave shape palladium platinum nucleocapsid is received
Meter Jing Ti, surfactant, etching agent, third weight of solvent ratio are 1:500:100:500.
Wherein, palladium source compound is ammonium chloropalladite, and platinum source compound is chloroplatinic acid；Surfactant is that molecular weight is
30000 polyvinylpyrrolidone；Surface capping agents are potassium bromide；Reducing agent is citric acid；First solvent and third solvent are
By weight the mixture of 1:1, the second solvent is n,N-Dimethylformamide for water and ethylene glycol；Etching agent is ferric acetate.
A kind of hollow platinum palladium nano-crystal body of inner concave shape, by the preparation method system of the hollow platinum palladium nano-crystal body of above-mentioned inner concave shape
?.
Performance test:
1. pattern test:
By inner concave shape palladium platinum core-shell nanocrystals made from indent palladium nano-crystal body made from step b) in embodiment 4, step c)
With its surface topography of surface sweeping transmission electron microscope observing of inner concave shape palladium platinum core-shell nanocrystals made from step d).
As shown in Figure 1, can be seen that the palladium nano-crystal body surface face that we prepare from transmission photo has apparent indent special
Sign, illustrates that the surface of palladium nano-crystal is made of high miller index surface；
As shown in Figure 2, it can be seen that from transmission photo after grown platinum shell, the surface of nanocrystal still maintains interior
Recessed structure feature, and surface is smooth, illustrates that platinum shell is also to be made of high miller index surface；
It is acted on from the figure 3, it may be seen that can be seen that from transmission electron microscope photo by chemical etching, intermediate palladium core is carved completely
Eating away has obtained hollow structure.The surface of the hollow structure still maintains the feature of concave inward structure simultaneously, shows by chemistry
The high miller index surface of platinum is still maintained after corrasion, and it is feasible for also illustrating that our this methods prepare high miller index surface
's；
As shown in Figure 4, clearer can see the surface of hollow structure clearly from dark field image photo is concave inward structure and transmittance structure
Photo the result is that coincide.
2. electrochemical redox performance test:
0.15 milligram is taken to be dispersed in 0.7 milliliter of distillation respectively the hollow platinum palladium nano-crystal body of inner concave shape made from above-described embodiment 4
Ultrasound obtains catalyst pulp in 30 minutes in water, 0.25 milliliter of isopropanol and 0.05 milliliter of naphthols mixed solution；Take 20 microlitres of slurries
Material uniformly drips to the electrode surface polished, and the area of electrode is 0.19625 square centimeter；Electrochemical workstation used is occasion
Magnificent electrochemical workstation, the equipment that rotating circular disk test macro is produced using Pine company, the U.S.；Take 0.1 mole every liter
High chloro acid solution is continually fed into nitrogen, does cyclic voltammetry curve until two adjacent curve weights under conditions of nitrogen saturation
It closes；Cyclic voltammetry curve is surveyed in 0.1 mole every liter of the perchloric acid solution that fresh nitrogen is saturated, then changes to oxygen saturation
0.1 mole every liter of high chloro acid solution tests its oxygen reduction performance, and 1600 rpms of electrode rotary speed, scanning speed
10 millivolts per second.Fig. 5 and Fig. 6 is respectively the hollow platinum palladium nano-crystal body catalyst of inner concave shape prepared by embodiment 4 in acid item
Cyclic voltammetry curve and hydrogen reduction curve under part.
As shown in Figure 5, which has apparent hydrogen adsorption/desorption peak in 0~0.4 volt of section, 0.6~
1.1 volts of sections are typical platinum oxidation reduction peaks, and the electrochemistry that can fit the nano material from the adsorption/desorption peak of hydrogen is living
Property area；
As Fig. 6 hydrogen reduction curve it is found that the half wave potential of the hollow platinum palladium nano-crystal body catalyst of inner concave shape made from us is
0.88 volt, the half wave potential of business platinum carbon is 0.86 volt, our half wave potentials of catalyst obtained are higher than business platinum carbon by 20
Millivolt is better than business platinum carbon catalyst.
It should be understood that those skilled in the art, can be improved or be become according to the above description
It changes, and all these modifications and variations should all belong to the protection domain of appended claims of the present invention.
Claims (10)
1. a kind of preparation method of the hollow platinum palladium nano-crystal body of inner concave shape, it is characterised in that the following steps are included:
A) it will be made after palladium source compound and surfactant, reducing agent, the first solvent and surface capping agents hybrid reaction and washing
Obtain palladium nano-crystal body；
B) it disperses palladium nano-crystal body in the first solvent, and palladium source compound, surfactant, reducing agent and surface packet is added
Indent palladium nano-crystal body is made after covering agent hybrid reaction；
C) it disperses indent palladium nano-crystal body in the second solvent, and surfactant, platinum source compound, reducing agent mixing is added
Inner concave shape palladium platinum core-shell nanocrystals are made after reacting and washing；
D) the hollow platinum palladium nano-crystal body of inner concave shape is made through chemical etching in inner concave shape palladium platinum core-shell nanocrystals.
2. a kind of preparation method of the hollow platinum palladium nano-crystal body of inner concave shape according to claim 1, it is characterised in that:
The step d) specifically, disperse inner concave shape palladium platinum core-shell nanocrystals in third solvent, be added surfactant,
Insulation reaction after etching agent mixing, the then hollow platinum palladium nano-crystal body of washed obtained inner concave shape.
3. a kind of preparation method of the hollow platinum palladium nano-crystal body of inner concave shape according to claim 1, it is characterised in that:
The palladium source compound is the compound containing chlorine Asia palladium acid group, and the platinum source compound is the chemical combination containing chloroplatinic acid root
Object.
4. a kind of preparation method of the hollow platinum palladium nano-crystal body of inner concave shape according to claim 1, it is characterised in that:
The surface capping agents are at least one of potassium bromide or aminated compounds.
5. a kind of preparation method of the hollow platinum palladium nano-crystal body of inner concave shape according to claim 1, it is characterised in that:
The reducing agent is ascorbic acid and its salt or at least one of citric acid and its salt.
6. a kind of preparation method of the hollow platinum palladium nano-crystal body of inner concave shape according to claim 2, it is characterised in that:
First solvent, the second solvent and the third solvent is respectively in water, N,N-dimethylformamide, ethylene glycol or methanol
At least one.
7. a kind of preparation method of the hollow platinum palladium nano-crystal body of inner concave shape according to claim 2, it is characterised in that:
The etching agent is to contain ferric iron compound.
8. a kind of preparation method of the hollow platinum palladium nano-crystal body of inner concave shape according to claim 7, it is characterised in that:
Described containing ferric iron compound is one of ferric trichloride, ferric sulfate, ferric nitrate or ferric acetate.
9. a kind of hollow platinum palladium nano-crystal body of inner concave shape, it is characterised in that:
The preparation method of the hollow platinum palladium nano-crystal body of its inner concave shape as described in claim 1~8 is made.
10. a kind of application of the hollow platinum palladium nano-crystal body of inner concave shape, it is characterised in that:
The hollow platinum-nickel alloys of inner concave shape as claimed in claim 9 are anti-as fuel battery negative pole oxygen reduction reaction, water-splitting
It answers, the catalyst application in acid oxygen reduction reaction or small organic molecule hydrogenation reaction.
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