CN105945277B - Onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle and preparation method thereof - Google Patents

Onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle and preparation method thereof Download PDF

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CN105945277B
CN105945277B CN201610326979.0A CN201610326979A CN105945277B CN 105945277 B CN105945277 B CN 105945277B CN 201610326979 A CN201610326979 A CN 201610326979A CN 105945277 B CN105945277 B CN 105945277B
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dihydroxy
fullerene
shell structure
benzoic acids
formaldehyde
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CN105945277A (en
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杨曦
付志兵
李佳
袁磊
赵海波
米睿
王朝阳
张厚琼
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Laser Fusion Research Center China Academy of Engineering Physics
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Laser Fusion Research Center China Academy of Engineering Physics
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/40—Carbon, graphite

Abstract

The invention provides a kind of onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle and preparation method thereof, the onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle of the present invention is so obtained, with 2,4 dihydroxy-benzoic acids, sodium hydroxide and formaldehyde are that raw material is configured to 2,4 dihydroxy-benzoic acid sodium formaldehyde solution, make it become colloidal sol by adjusting solution ph, and colloidal sol is stood and obtains gel, then 2,4 dihydroxy-benzoic acid sodium formaldehyde gels are put into containing Pd2+Palladium salt solution in soak, carry out ion exchange, obtain being loaded with Pd2+2,4 dihydroxy-benzoic acid formaldehyde gels, be loaded with Pd by described2+2, after 4 dihydroxy-benzoic acid formaldehyde gels are ground into gel powder and are heated to 950 1500 DEG C in the mixed atmosphere of oxygen and inert gas, cooled in the atmosphere of pure inert gas, so as to obtain onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle.

Description

Onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle and preparation method thereof
Technical field
The present invention relates to nano-particle preparation field, more particularly to a kind of onion-like fullerene cladding Metal Palladium core shell structure Nano-particle and preparation method thereof.
Background technology
Metal Pd nano particle is very good catalyst, is being widely used in organic matter hydrogenation dehydrogenation reaction, oil Refining, purifying vehicle exhaust, high power-fuel cell etc..Meanwhile nanometer Pd material is in hydrogen storage, chemical sensor etc. Have and be quite widely applied.However, single Pd nano particle less stable, is easy to reunion and grows up and flow in use Lose, cause the change of its property and the decline of performance.In nano-particle outer layer covers up-protective layer, can make palladium particle mutually every From can not sinter and grow up, environmental stability is more preferable.It is additionally, since protective layer and also changes the original property of palladium particle, makes its tool Have and be more widely applied.
Onion-like fullerene is a kind of fullerene carbon material with special hollow cage structure, is nano-particle protection The good selection of separation layer, it has advantages below：Acidproof, alkaline-resisting, chemical property stabilization, it is easier to reclaim catalyst gold Category, is advantageous to environmental protection etc..
At present, the research of relevant onion-like fullerene cladding Pd nano particle is less.University of Alabama of the U.S. The research of related fields was done by Chopra seminars, and its method used is first to carry out Pd nano particle with oxygen plasma Surface oxidation, chemical deposition is recycled to grow carbon-coating in particle surface, so as to obtain onion shape multilayer fullerene Coated with Palladium core Shell structural nano particle.Because this method is to grow carbon to Pd nano particle surface oxidation and chemical deposition with oxygen plasma Layer, is respectively necessary for different special instruments, cause to prepare it is costly, moreover, the core shell structure prepared by this kind of method The carbon-coating on its surface of nano-particle is relatively thin, and crystallinity is poor.
The content of the invention
It is an object of the present invention to provide a kind of onion-like fullerene for preparing to coat Metal Palladium core-shell structure nanometer particle Method, it can realize that preparation technology is simple, low to the less demanding of experiment condition, cost, and can prepare carbon-coating knot Brilliant good onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of method for preparing onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle, comprises the following steps：
2,4- dihydroxy-benzoic acids and sodium hydroxide are dissolved in deionized water and are configured to add formaldehyde after solution, stirs shape Into 2,4- dihydroxy-benzoic acids sodium-formalin, sodium hydroxide pH value regulator regulation 2,4- dihydroxy-benzoic acids are then added The pH value of sodium-formalin, until becoming 2,4- dihydroxy-benzoic acids sodium-formaldehyde colloidal sol；
2,4- dihydroxy-benzoic acids sodium-formaldehyde colloidal sol is stood, coagulated so as to obtain 2,4- dihydroxy-benzoic acids sodium-formaldehyde Glue；
2,4- dihydroxy-benzoic acids sodium-formaldehyde gel is put into containing Pd2+Palladium salt solution in soak, carry out ion exchange, Obtain being loaded with Pd2+2,4- dihydroxy-benzoic acids-formaldehyde gel；
Pd will be loaded with2+2,4- dihydroxy-benzoic acids-formaldehyde gel be ground into gel powder and in oxygen and inert gas Heated in mixed atmosphere, when temperature rises to 950-1200 DEG C, cooled in the atmosphere of pure inert gas, obtain onion shape Fullerene coats Metal Palladium core-shell structure nanometer particle.
Another object of the present invention is to, there is provided a kind of onion-like fullerene coats Metal Palladium core-shell structure nanometer particle, Its surface can form thicker carbon-coating structure, and carbon-coating crystallinity is good.
To achieve the above object, onion-like fullerene of the invention cladding Metal Palladium core-shell structure nanometer particle is according to upper State what step was prepared.And the concrete structure of the onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle of the present invention It is that metal Pd nano particle is core, core outer cladding onion-like fullerene shell, shell has 10-50nm thickness.
The advantageous effects of the present invention：
The present invention is configured to 2,4- dihydroxy-benzoic acids by raw material of 2,4- dihydroxy-benzoic acids, sodium hydroxide and formaldehyde Sodium-formalin, 2,4- dihydroxy-benzoic acids sodium-formalin is passed sequentially through and adds sodium hydroxide pH value regulator, stand Step, 2,4- dihydroxy-benzoic acids sodium-formaldehyde gel is obtained, then 2,4- dihydroxy-benzoic acids sodium-formaldehyde gel is put into and contained There is Pd2+Palladium salt solution in immersion carry out ion exchange, so as to obtain being loaded with Pd2+2,4- dihydroxy-benzoic acids-formaldehyde coagulate Glue, it then will be loaded with Pd2+2,4- dihydroxy-benzoic acids-formaldehyde gel be ground into gel powder and in the mixed of oxygen and inert gas Close and heated in atmosphere, when temperature rises to 950-1200 DEG C, cooled in the atmosphere of pure inert gas, so as to obtain onion Shape fullerene coats Metal Palladium core-shell structure nanometer particle.The preparation technology of the present invention is simple, it is only necessary to is loaded with what is prepared Pd2+2,4- dihydroxy-benzoic acids-formaldehyde gel be ground into gel powder and heated in the mixed atmosphere of oxygen and inert gas Reaction, after cooling, so that it may obtain onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle.In whole preparation process, Requirement to laboratory apparatus and reaction condition is not high, without using the experimental facilities or equipment of costliness, reduces and is prepared into This, also, the onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle size of the present invention is more uniform, and yield is high, generation Carbon-coating well-crystallized.
Brief description of the drawings
Fig. 1 is the process chart for preparing onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle of the present invention；
The onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle that Fig. 2 (a) is the present invention is seen under ESEM The shape appearance figure observed；
The onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle that Fig. 2 (b) is the present invention is seen under ESEM The local shape appearance figure observed；
The onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle that Fig. 3 (a) is the present invention is seen under transmission electron microscope The structure chart of the shell observed；
The onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle that Fig. 3 (b) is the present invention is seen under transmission electron microscope The structure chart of the shell observed；
The onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle that Fig. 3 (c) is the present invention is seen under transmission electron microscope The structure chart of the nucleocapsid region observed；
Fig. 3 (d) is the onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle of the present invention with electron energy mistake Filter the distribution diagram of element of the nucleocapsid region of stave sign；
Fig. 4 (a) is the shape appearance figure that the Pd nano particle prepared in pure argon atmosphere is observed under ESEM；
Fig. 4 (b) is the local pattern that the Pd nano particle prepared in pure argon atmosphere is observed under ESEM Figure；
Fig. 5 (a) is that the Pd nano particle that oxygen concentration is prepared under conditions of being 0.5% in mixed atmosphere is electric in scanning The shape appearance figure that Microscopic observation arrives；
Fig. 5 (b) is that the Pd nano particle that oxygen concentration is prepared under conditions of being 1.0% in mixed atmosphere is electric in scanning The shape appearance figure that Microscopic observation arrives；
Fig. 5 (c) is that the Pd nano particle that oxygen concentration is prepared under conditions of being 1.5% in mixed atmosphere is electric in scanning The shape appearance figure that Microscopic observation arrives；
Fig. 5 (d) is that the Pd nano particle that oxygen concentration is prepared under conditions of being 2.0% in mixed atmosphere is electric in scanning The shape appearance figure that Microscopic observation arrives；
Fig. 6 (a) is that the Pd nano particle prepared under conditions of heating-up temperature is 950 DEG C is observed under ESEM Shape appearance figure；
Fig. 6 (b) is that the Pd nano particle prepared under conditions of heating-up temperature is 850 DEG C is observed under ESEM Shape appearance figure；
Fig. 6 (c) is that the Pd nano particle prepared under conditions of heating-up temperature is 750 DEG C is observed under ESEM Shape appearance figure；
Fig. 6 (d) is that the Pd nano particle prepared under conditions of heating-up temperature is 650 DEG C is observed under ESEM Shape appearance figure；
Fig. 7 (a) is when temperature reaches 1050 DEG C, is incubated the shape that the Pd nano particle after 1h is observed under ESEM Looks figure；
Fig. 7 (b) is when temperature reaches 1050 DEG C, is incubated the shape that the Pd nano particle after 2h is observed under ESEM Looks figure；
Fig. 7 (c) is when temperature reaches 1050 DEG C, is incubated the shape that the Pd nano particle after 3h is observed under ESEM Looks figure；
Fig. 8 (a) is to be heated to the Pd nano particle prepared under conditions of 1050 DEG C by 17.5 DEG C/min of the rate of heat addition The shape appearance figure observed under ESEM；
Fig. 8 (b) is being swept by the Pd nano particle that 9 DEG C/min is heated to prepare under conditions of 1050 DEG C of the rate of heat addition Retouch the shape appearance figure observed under Electronic Speculum；
Fig. 8 (c) is being swept by the Pd nano particle that 9 DEG C/min is heated to prepare under conditions of 1050 DEG C of the rate of heat addition Retouch the shape appearance figure observed under Electronic Speculum；
Fig. 9 is the signal of the growth mechanism of the onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle of the present invention Figure.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment Condition person, the condition suggested according to normal condition or manufacturer are carried out.Agents useful for same or the unreceipted production firm person of instrument, it is The conventional products that can be obtained by commercially available purchase.
For ease of it will be appreciated by those skilled in the art that existing some terms or abbreviation to being related in the present invention illustrate：
Sodium hydroxide pH value regulator：Refer to the hydrogen-oxygen for adjusting 2,4- dihydroxy-benzoic acids sodium-formalin pH value Change sodium solution.Its solution concentration present invention is not particularly limited, and those skilled in the art can be according to actual conditions reasonable selection The sodium hydroxide solution of suitable concn.
Formaldehyde：The present invention uses in general commercialization formaldehyde, is liquid, concentration is about 38wt%.
DF：2,4-Dihydroxybenzoic acid-Formalin, 2,4- dihydroxy-benzoic acids-formaldehyde.
NPs：Nano Particles, nano-particle.
CDF：Carbon-2,4-Dihydroxybenzoic acid-Formalin, 2, the 4- dihydroxy-benzoic acids of carbonization- Formaldehyde
Pd-DF：Pd-2,4-Dihydroxybenzoic acid-Formalin are loaded with Pd2+2,4- dihydroxy-benzoic acids- Formaldehyde
The method for preparing onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle of the present invention comprises the following steps：
Step 1：Prepare 2,4- dihydroxy-benzoic acids sodium-formaldehyde colloidal sol
2,4- dihydroxy-benzoic acids and sodium hydroxide are dissolved in deionized water and are configured to solution, then adds formaldehyde, is stirred Mix to form 2,4- dihydroxy-benzoic acids sodium-formalin；Add sodium hydroxide pH value regulator regulation 2,4- dihydroxy benzenes first The pH value of sour sodium-formalin, until becoming 2,4- dihydroxy-benzoic acids sodium-formaldehyde colloidal sol.
Preferably, by 2,4- dihydroxy-benzoic acids, sodium hydroxide and formaldehyde according to 1:1:4 molar ratio is into 2,4- bis- Hydroxybenzoic acid sodium-formalin, and adjusted solution ph to 7-9 by sodium hydroxide pH value regulator, then spend Ionized water dilutes.
Step 2：Prepare 2,4- dihydroxy-benzoic acids sodium-formaldehyde gel
2,4- dihydroxy-benzoic acids sodium-formaldehyde colloidal sol is stood, coagulated so as to obtain 2,4- dihydroxy-benzoic acids sodium-formaldehyde Glue.
Preferably, 2,4- dihydroxy-benzoic acids sodium-formaldehyde colloidal sol stands 3-8 days at a temperature of 50-70 DEG C.Temperature Gao Jing It is short to put the time, the low time of repose length of temperature.The density of the 2,4- dihydroxy-benzoic acids sodium-formaldehyde gel obtained is 0.1- 0.3g/ml。
Step 3：Preparation is loaded with Pd2+2,4- dihydroxy-benzoic acids-formaldehyde gel
2,4- dihydroxy-benzoic acids sodium-formaldehyde gel is put into containing Pd2+Palladium salt solution in soak, carry out ion exchange, Obtain being loaded with Pd2+2,4- dihydroxy-benzoic acids-formaldehyde gel.
Preferably, by 2,4- dihydroxy-benzoic acids sodium-formaldehyde gel and containing Pd2+Palladium salt solution according to 1:4 volume ratio 20-30h is soaked, is soaked 3-5 times.Containing Pd2+The density of palladium salt solution be 0.5-3g/L.Containing Pd2+Palladium salt solution be, for example, PdCl2Solution, PdSO4Solution or Pd (NO3)2Solution.
Step 4：Prepare onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle
Pd will be loaded with2+2,4- dihydroxy-benzoic acids-formaldehyde gel be ground into gel powder, by gel powder in oxygen and inertia Heated in the mixed atmosphere of gas, when temperature rises to 950-1200 DEG C, cool, obtain in the atmosphere of pure inert gas Onion-like fullerene coats Metal Palladium core-shell structure nanometer particle.
Preferably, it is 5-20 DEG C/min in oxygen and the gaseous mixture of inert gas using the rate of heat addition by the gel powder after grinding 1000-1200 DEG C is heated in atmosphere.Percent by volume in mixed atmosphere shared by oxygen is 0.1%-0.5%.Indifferent gas Style helium, xenon or argon gas in this way.
According to the method described above, the onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle of the present invention is prepared.
Embodiment 1
Mol ratio according to 2,4- dihydroxy-benzoic acids, sodium hydroxide and formaldehyde is 1：1：4 ratio prepares volume 100mL, density 0.1g/mL 2,4- dihydroxy-benzoic acids sodium-formaldehyde gel, wherein, 2,4- dihydroxy-benzoic acid sodium-formaldehyde coagulates The density of glue is that the quality divided by 2,4- dihydroxy-benzoic acids sodium-formalin of formaldehyde are added by 2,4- dihydroxy-benzoic acids sodium What volume obtained.
2,4- dihydroxy-benzoic acids 5.2g and sodium hydroxide 1.35g are first dissolved in deionized water, now deionized water used Volume to be advisable no more than 70mL, be configured to solution.2,4- dihydroxy-benzoic acids and sodium hydroxide reaction generation 2,4- dihydroxies Yl benzoic acid sodium, so as to obtain 2,4- dihydroxy-benzoic acid sodium solutions.
The formalin 10mL that concentration is about 38wt% is added in 2,4- dihydroxy-benzoic acid sodium solutions, is stirred, Form light yellow transparent liquid.With the pH value of sodium hydroxide pH value regulator regulation 2,4- dihydroxy-benzoic acids sodium-formalin To 7.Deionized water is added, total liquid volume is stirred to 100mL, it is molten is obtained 2,4- dihydroxy-benzoic acids sodium-formaldehyde Glue.
2, the 4- dihydroxy-benzoic acids sodium-formaldehyde colloidal sol prepared is fitted into closed container, it is quiet at a temperature of 50 DEG C Put 8 days, form brownish red clear gel, as 2,4- dihydroxy-benzoic acids sodium-formaldehyde gel.
2,4- dihydroxy-benzoic acids sodium-formaldehyde gel is taken out, it is 0.5-1cm to be cut into volume3It is 1.5g/ that fritter, which is put into density, L, volume is 400ml PdSO420h is soaked in solution, carries out ion exchange, soaks 3 times, obtains being loaded with Pd2+2,4- dihydroxies Yl benzoic acid-formaldehyde gel.It is loaded with Pd2+2,4- dihydroxy-benzoic acids-formaldehyde gel for rufous, opaque gel.And And the gel is at normal temperatures brittle substance, can directly be pulverized.
Pd will be loaded with2+2,4- dihydroxy-benzoic acids-formaldehyde gel be ground into gel powder.By gel powder in oxygen and helium Mixed atmosphere in heat, and temperature is risen to 1000 DEG C with the 10 DEG C/min rate of heat addition.Wherein, oxygen in mixed atmosphere Concentration is 0.1%.After temperature rises to 1000 DEG C, by the powder after heating response, natural cooling drops in the atmosphere of pure helium Temperature, that is, obtain onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle.
Embodiment 2
Mol ratio according to 2,4- dihydroxy-benzoic acids, sodium hydroxide and formaldehyde is 1：1：4 ratio prepares volume 100mL, density 0.3g/mL 2,4- dihydroxy-benzoic acids sodium-formaldehyde gel, wherein, 2,4- dihydroxy-benzoic acid sodium-formaldehyde coagulates The density of glue is that the quality divided by 2,4- dihydroxy-benzoic acids sodium-formalin of formaldehyde are added by 2,4- dihydroxy-benzoic acids sodium What volume obtained.
2,4- dihydroxy-benzoic acids 15.6g and sodium hydroxide 4.06g are first dissolved in deionized water, now deionized water used Volume to be advisable no more than 50mL, be configured to solution.2,4- dihydroxy-benzoic acids and sodium hydroxide reaction generation 2,4- dihydroxies Yl benzoic acid sodium, so as to obtain 2,4- dihydroxy-benzoic acid sodium solutions.
The formalin 32mL that concentration is about 38wt% is added in 2,4- dihydroxy-benzoic acid sodium solutions, is stirred, Form light yellow transparent liquid.With the pH value of sodium hydroxide pH value regulator regulation 2,4- dihydroxy-benzoic acids sodium-formalin To 9.Deionized water is added, total liquid volume is stirred to 100mL, it is molten is obtained 2,4- dihydroxy-benzoic acids sodium-formaldehyde Glue.
2, the 4- dihydroxy-benzoic acids sodium-formaldehyde colloidal sol prepared is fitted into closed container, it is quiet at a temperature of 70 DEG C Put 3 days, form brownish red clear gel, as 4- dihydroxy-benzoic acids sodium-formaldehyde gel.
2,4- dihydroxy-benzoic acids sodium-formaldehyde gel is taken out, it is 0.5-1cm to be cut into volume3Fritter be put into density for 3g/L, Volume is 400ml PdCl230h is soaked in solution, carries out ion exchange, soaks 5 times, obtains being loaded with Pd2+2,4- dihydroxy Benzoic acid-formaldehyde gel.It is loaded with Pd2+2,4- dihydroxy-benzoic acids-formaldehyde gel for rufous, opaque gel.And The gel is at normal temperatures brittle substance, can directly be pulverized.
Pd will be loaded with2+2,4- dihydroxy-benzoic acids-formaldehyde gel be ground into gel powder.By gel powder in oxygen and xenon Mixed atmosphere in heat, and temperature is risen to 1200 DEG C with the 20 DEG C/min rate of heat addition.Wherein, oxygen in mixed atmosphere Concentration is 0.3%.After temperature rises to 1200 DEG C, by the powder after heating response, natural cooling drops in the atmosphere of pure xenon Temperature, that is, obtain onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle.
Embodiment 3
Mol ratio according to 2,4- dihydroxy-benzoic acids, sodium hydroxide and formaldehyde is 1：1：4 ratio prepares volume 100mL, density 0.2g/mL 2,4- dihydroxy-benzoic acids sodium-formaldehyde gel, wherein, 2,4- dihydroxy-benzoic acid sodium-formaldehyde coagulates The density of glue is that the quality divided by 2,4- dihydroxy-benzoic acids sodium-formalin of formaldehyde are added by 2,4- dihydroxy-benzoic acids sodium What volume obtained.
2,4- dihydroxy-benzoic acids 8.0198g and sodium hydroxide 2.082g are first dissolved in deionized water, now spend from The volume of sub- water is configured to solution to be advisable no more than 70mL.2,4- dihydroxy-benzoic acids and sodium hydroxide reaction generation 2,4- Dihydroxy-benzoic acid sodium, so as to obtain 2,4- dihydroxy-benzoic acid sodium solutions.
The formalin 15.43mL that concentration is about 38wt% is added in 2,4- dihydroxy-benzoic acid sodium solutions, stirring is equal It is even, form light yellow transparent liquid.With the pH of sodium hydroxide pH value regulator regulation 2,4- dihydroxy-benzoic acids sodium-formalin It is worth 8.Deionized water is added, total liquid volume is stirred to 100mL, is obtained 2,4- dihydroxy-benzoic acids sodium-formaldehyde Colloidal sol.
2, the 4- dihydroxy-benzoic acids sodium-formaldehyde colloidal sol prepared is fitted into closed container, it is quiet at a temperature of 60 DEG C Put 7 days, form brownish red clear gel, as 4- dihydroxy-benzoic acids sodium-formaldehyde gel.
2,4- dihydroxy-benzoic acids sodium-formaldehyde gel is taken out, it is 0.5-1cm to be cut into volume3Fritter be put into density for 2g/L, Volume is 400ml PdCl224h is soaked in solution, carries out ion exchange, soaks 4 times, obtains being loaded with Pd2+2,4- dihydroxy Benzoic acid-formaldehyde gel.It is loaded with Pd2+2,4- dihydroxy-benzoic acids-formaldehyde gel for rufous, opaque gel.And The gel is at normal temperatures brittle substance, can directly be pulverized.
Pd will be loaded with2+2,4- dihydroxy-benzoic acids-formaldehyde gel be ground into gel powder.By gel powder in oxygen and argon gas Mixed atmosphere in heat, and temperature is risen to 1050 DEG C with the 17.5 DEG C/min rate of heat addition.Wherein, oxygen in mixed atmosphere Concentration be 0.5%.After temperature rises to 1050 DEG C, by the powder after heating response in the atmosphere of pure argon natural cooling Cooling, that is, obtain onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle.
Fig. 2 (a) to Fig. 3 (d) is the test result of embodiment 3.
Referring to Fig. 2 (a), a large amount of onion-like fullerene cladding Metal Palladium core-shell structure nanometer particles, grain are generated in sample Footpath has some particles to flock together from tens of to hundreds of nanometers.Carbon skeleton has been not observed in Fig. 2 (a) to deposit .Fig. 2 (b) is the Local map after Fig. 2 (a) amplifications, from Fig. 2 (b) it will be clear that onion-like fullerene coats Metal Palladium Core-shell structure nanometer particle has core shell structure, and shell is clear, and thickness is in 10-50nm or so.
Referring to Fig. 3 (a) to Fig. 3 (d), the onion-like fullerene cladding Metal Palladium core shell structure observed under transmission electron microscope The core shell structure of nano-particle.By Fig. 3 (a) and Fig. 3 (b), it can be seen that, shell layer lattice structure is in clearly onion shape multilayer Structure, spacing of lattice 0.33nm, (002) crystal face of hexagonal phase carbon can be demarcated as, coincide with the interlamellar spacing of graphite.Referring to figure 3 (a), the spacing of lattice of kernel is 0.21nm, is demarcated as (111) crystal face of Emission in Cubic palladium.This explanation core shell structure is onion shape Orderly carbon-coating cladding metal Pd nano particle (Pd C).
As shown in Fig. 3 (a) and Fig. 3 (b), the variable thickness of the multilayer Fullerene Carbon shell of different particles, in Fig. 3 (a) Carbon shell only has 10 layers or so, thickness about 4nm；The carbon shell of particle has 60 layers in Fig. 3 (b), and thickness is at least 20nm.
Meanwhile it is completely embedded, palladium from Fig. 3 (a) it is observed that Metal Palladium kernel and carbon shell core-shell interface are clear Lattice and carbon lattice be directly connected to substantially, it is very close to each other.This explanation carbon is directly to be grown on palladium core surface.Also, The lattice of palladium oxide is not observed in interface, illustrates no generation palladium oxide after the completion of reaction.
Further to verify above-mentioned analysis, the present inventor composes (ELLS) with electron energy filter and characterizes nucleocapsid knot The Elemental redistribution in structure region.Fig. 3 (d) distribution diagram of element intuitively illustrates Pd@C core shell structures, wherein Pd and C element distribution The core shell structure that shape and Fig. 3 (c) scanning electron microscope (SEM) photograph are shown is basically identical, and Pd elements are mainly distributed on kernel, and C element is formed Outer shell.Wherein, the O elements between palladium kernel and carbon shell are mainly derived from Pd nano-particles outer layer and adsorbed in atmosphere Oxygen.
Comparative example 1-4 is based on embodiment 3, and research different condition is to generation onion-like fullerene cladding metal The influence of palladium core-shell structure nanometer particle.
Comparative experimental example 1
This comparative experimental example is based on embodiment 3, have studied and is loaded with Pd2+2,4- dihydroxy-benzoic acids-formaldehyde coagulate Response situation of the rubber powder under the conditions of oxygen-free atmosphere.Its result is as follows：
Referring to Fig. 4 (a) and Fig. 4 (b), it is the test result of comparative example.The sample prepared under pure argon atmosphere, Shown in its shape appearance figure under ESEM such as Fig. 4 (a), Pd nano particle is distributed evenly in carbon skeleton.This explanation, is entering During row ion exchange, in Pd-DF gels, Pd2+Equably it is supported on organic backbone.Local pattern according to shown by Fig. 4 (b) Scheme, do not observe the Pd nano particle with core shell structure in the sample of comparative example, Pd nano particle is distributed in carbon skeleton On.This is illustrated, the Pd nano particle with core shell structure can not be prepared in the environment of pure argon (anaerobic), in other words, Oxygen has the function that key to growth Pd@C core-shell structure nanometer particles.
Comparative experimental example 2
This test example have studied different oxygen concentrations to generation onion-like fullerene cladding Metal Palladium nuclear shell structure nano grain The influence of son.
Referring to Fig. 5 (a) to Fig. 5 (d), under different oxygen concentrations, the shape appearance figure of the sample arrived by scanning electron microscope observation. The sample prepared in oxygen concentration 0.5% is mainly the core shell structure particle of carbon-coating cladding, as shown in Fig. 5 (a).With oxygen Concentration increases to 1.0%, and carbon-based is reacted, and product is mainly the accumulation of palladium particle, does not observe cladding outside particle be present Shell, as shown in Fig. 5 (b).Oxygen concentration continues to increase, and to more than 1.5%, does not see carbon, hence it is evident that it was observed that palladium particle merges Grow up, stephanoporate framework is formed, such as Fig. 5 (c) and Fig. 5 (d).
Therefore, oxygen concentration is very big on influences such as product morphology structures in reaction atmosphere, and oxygen concentration can not be too high, with 0.1%-0.5% is advisable.
Comparative experimental example 3
Originally test example and have studied different heating temperature to generation onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle Influence.
Referring to Fig. 6 (a) to Fig. 6 (d), at different temperatures, the shape appearance figure of the sample arrived by scanning electron microscope observation.Fig. 6 (a) it is the shape appearance figure under the conditions of 950 DEG C；Fig. 6 (b) is the shape appearance figure under the conditions of 850 DEG C；Fig. 6 (c) is the shape under the conditions of 750 DEG C Looks figure；Fig. 6 (d) is the shape appearance figure under the conditions of 650 DEG C.
As can be seen that 950 DEG C and following temperature can not grow onion-like fullerene carbon coating layer.950 DEG C -750 DEG C three The change of size unobvious of the Pd nano particle synthesized at individual temperature, around there is carbon skeleton isolation, and at 650 DEG C, carbon skeleton is bright Aobvious reaction is more, and palladium particle aggregation is grown up.This is probably because carbon easily causes with oxygen reaction at 650 DEG C.
Therefore, the heating-up temperature for preparing onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle should be at 950 DEG C More than.
Comparative experimental example 4
Originally test example to have studied when temperature is heated to 1050 DEG C, different soaking times are to generation onion-like fullerene cladding gold Belong to the influence of palladium core-shell structure nanometer particle.
Referring to Fig. 7 (a) to Fig. 7 (c), under different soaking times, the shape appearance figure of the sample arrived by scanning electron microscope observation. Fig. 7 (a) is insulation 1h shape appearance figure；Fig. 7 (b) is insulation 2h shape appearance figure；Fig. 7 (c) is insulation 3h shape appearance figure.
The sample prepared under different soaking times contains spherical Pd nano particle, particle diameter heterogeneity.This explanation exists In temperature-rise period, particle has grown substantially to be finished, and to not having regrowth substantially during insulation, soaking time length influences not on it Greatly.Therefore incubation step is not carried out in the preparation method of the present invention.
Comparative experimental example 5
Originally test example and have studied different heating rates to generation onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle Influence.
Referring to Fig. 8 (a) to Fig. 8 (c), under the rate of heat addition, the shape appearance figure of the sample arrived by scanning electron microscope observation.Fig. 8 (a) it is to heat the shape appearance figure for making temperature rise to 1050 DEG C by 17.5 DEG C/min of the rate of heat addition；Fig. 8 (b) and Fig. 8 (c) is heating Speed is that 9 DEG C/min heating makes the shape appearance figure that temperature rises to 1050 DEG C.
It can be seen that the fast sample of the rate of heat addition is substantially core shell structure particle, and the heat time is grown, heating speed The shell carbon-coating and oxygen for then having some particles in the slow sample of rate react, and form the aggregate of palladium particle.
Based on above-mentioned test result, inventor prepares onion-like fullerene cladding Metal Palladium nuclear shell structure nano to the present invention The method of particle provides the growth machine of following reaction mechanism, i.e. onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle System.
Referring to Fig. 9, in the ion exchange process of step 3, Pd2+Na is replaced by ion exchange+It is supported on 2,4- dihydroxies In the skeleton of yl benzoic acid-formaldehyde gel, and it is evenly distributed, this can be prepared Pd nano particle (Fig. 4 (b) in sample by anaerobic Shown in) be evenly distributed in carbon skeleton and verify.In step 4, to being loaded with Pd2+2,4- dihydroxy-benzoic acids-formaldehyde gel Powder heats in the mixed atmosphere of oxygen and argon gas, 2,4- dihydroxy-benzoic acids-formaldehyde gel molecule be decomposed into organic molecule, CO2、CH4、H2O etc..Due to during heating response, reaction reproducibility is stronger, by C by Pd2+It is reduced to Metal Palladium, aggregation life A length of Pd nano particle.Pd nano particle surface and the oxygen reaction in mixed atmosphere, generate Pd oxidation state mixture.Pd's Oxide is simultaneously not bery stable, can decompose generation simple substance Pd at high temperature.Therefore when reaction temperature further improves, palladium nanoparticle The C in organic molecule around sub provides electronics, generation simple substance C；Pd peroxide breaks down simultaneously, receiving are electronically generated metal Pd.So as to which, carbon is in Pd nano particle superficial growth, multilayer fullerene clad is formed, is finally grown to serve as Pd@C nano particles.
It is pure inert atmosphere as reacted, Pd nanoparticle surfaces will not form oxide layer, therefore will not shape in anaerobic reaction It is nucleated shell structure particle.In oxidizing atmosphere, oxygen can be touched positioned at skeleton surface and neighbouring Pd particles, causes ocean The growth of green onion shape fullerene carbon-coating.
Although illustrate and describing the present invention with specific embodiment, but will be appreciated that without departing substantially from the present invention's Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims Including belonging to all such changes and modifications in the scope of the invention.

Claims (10)

  1. A kind of 1. method for preparing onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle, it is characterised in that the side Method comprises the following steps：
    2,4- dihydroxy-benzoic acids and sodium hydroxide are dissolved in deionized water and are configured to add formaldehyde after solution, stirring is formed 2,4- dihydroxy-benzoic acid sodium-formalin, then add sodium hydroxide pH value regulator and adjust 2, the 4- dihydroxy benzenes first The pH value of sour sodium-formalin, until becoming 2,4- dihydroxy-benzoic acids sodium-formaldehyde colloidal sol；
    2, the 4- dihydroxy-benzoic acids sodium-formaldehyde colloidal sol is stood, coagulated so as to obtain 2,4- dihydroxy-benzoic acids sodium-formaldehyde Glue；
    The 2,4- dihydroxy-benzoic acids sodium-formaldehyde gel is put into containing Pd2+Palladium salt solution in soak, carry out ion exchange, Obtain being loaded with Pd2+2,4- dihydroxy-benzoic acids-formaldehyde gel；
    Pd is loaded with by described2+2,4- dihydroxy-benzoic acids-formaldehyde gel be ground into gel powder and in oxygen and inert gas Heated in mixed atmosphere, when temperature rises to 950-1200 DEG C, cooled in the atmosphere of pure inert gas, obtain onion shape Fullerene coats Metal Palladium core-shell structure nanometer particle.
  2. 2. the method according to claim 1 for preparing onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle, its It is characterised by, by 2, the 4- dihydroxy-benzoic acids, the sodium hydroxide and the formaldehyde according to 1:1:4 molar ratio into 2, the 4- dihydroxy-benzoic acids sodium-formalin, and add the sodium hydroxide pH value regulator and adjust solution ph To 7-9, then diluted with deionized water.
  3. 3. the method according to claim 1 for preparing onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle, its It is characterised by, 2, the 4- dihydroxy-benzoic acids sodium-formaldehyde colloidal sol stands 3-8 days at a temperature of 50-70 DEG C.
  4. 4. the method according to claim 1 for preparing onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle, its It is characterised by, the density of 2, the 4- dihydroxy-benzoic acids sodium-formaldehyde gel is 0.1-0.3g/mL.
  5. 5. the method according to claim 1 for preparing onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle, its It is characterised by, by 2, the 4- dihydroxy-benzoic acids sodium-formaldehyde gel and described contains Pd2+Palladium salt solution according to 1:4 volume Than immersion.
  6. 6. the method according to claim 5 for preparing onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle, its It is characterised by, 2, the 4- dihydroxy-benzoic acids sodium-formaldehyde gel, which is put into, described contains Pd2+Palladium salt solution in soak 3-5 times, often Secondary immersion 20-30h.
  7. 7. the method according to claim 5 for preparing onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle, its It is characterised by, it is described to contain Pd2+The density of palladium salt solution be 0.5-3g/L.
  8. 8. the method according to claim 1 for preparing onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle, its It is characterised by, the gel powder after grinding is heated to 950-1200 in the mixed atmosphere of oxygen and inert gas DEG C, the rate of heat addition is 5-20 DEG C/min.
  9. 9. the method according to claim 8 for preparing onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle, its It is characterised by, the percent by volume in the mixed atmosphere shared by oxygen is 0.1%-0.5%.
  10. 10. a kind of onion-like fullerene coats Metal Palladium core-shell structure nanometer particle, it is characterised in that the nano-particle is root Prepared according to the method for preparing onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle described in one of claim 1 to 9 's.
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