CN105945277A - Onion-shaped fullerene clad metal palladium core shell structure nano-particle and preparation method thereof - Google Patents
Onion-shaped fullerene clad metal palladium core shell structure nano-particle and preparation method thereof Download PDFInfo
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Abstract
The invention provides an onion-shaped fullerene clad metal palladium core shell structure nano-particle and a preparation method thereof. The onion-shaped fullerene clad metal palladium core shell structure nano-particle is prepared as follows: 2, 4-dihydroxyl sodium benzoate-formaldehyde solution is prepared with 2, 4-dihydroxy-benzoic acid, sodium hydroxide and formaldehyde as raw materials, and is changed to sol through adjusting the pH value thereof; the sol is stood to obtain gel; then, 2, 4-dihydroxyl sodium benzoate-formaldehyde gel is put in Pd2+ contained palladium salt solution to dip for ion exchange to obtain Pd2+ carried 2, 4-dihydroxyl sodium benzoate-formaldehyde gel; and the Pd2+ carried 2, 4-dihydroxyl sodium benzoate-formaldehyde gel is grinded to gel powder for heating to 950-1500 DEG C in a mixed atmosphere of oxygen and inert gas, and is cooled in a pure inert gas atmosphere to obtain the onion-shaped fullerene clad metal palladium core shell structure nano-particle.
Description
Technical field
The present invention relates to nanoparticle preparation field, particularly relate to a kind of onion-like fullerene cladding metal
Palladium core-shell structure nanometer particle and preparation method thereof.
Background technology
Metal Palladium nanoparticle is the best catalyst, is being widely used in Organic substance hydrogenation dehydrogenation
The aspects such as reaction, petroleum refining, purifying vehicle exhaust, high power-fuel cell.Meanwhile, palladium nanometer material
Expect also to have at the aspect such as hydrogen storage, chemical sensor to be quite widely applied.But, single palladium nanometer
Particle stability is poor, is in use easy to reunion and grows up and run off, cause its character change and
The decline of performance.At nanoparticle outer layer covers up-protective layer, palladium particle can be made mutually isolated, nothing
Method sintering is grown up, and environmental stability is more preferable.Being additionally, since protective layer, also to change palladium particle original
Character so that it is have and be more widely applied.
Onion-like fullerene is the fullerene material with carbon element that a class has special hollow cage structure, is to receive
The good selection of rice corpuscles protecting insulating layer, it has the advantage that acidproof, alkaline-resisting, chemical property
Stable, it is easier to reclaim catalyst metals, beneficially environmental protection etc..
At present, the research about onion-like fullerene Coated with Palladium nanoparticle is less.U.S. Alabama
The research of related fields was done by the Chopra seminar of university, and its method used is, first by palladium nanometer
Particle oxygen plasma carries out surface oxidation, and recycling chemical deposition grows carbon-coating at particle surface,
Thus obtain Bulbus Allii Cepae shape multilamellar fullerene Coated with Palladium core-shell structure nanometer particle.Owing to the method is to use oxygen
Plasma grows carbon-coating to Pd nano particle surface oxidation and chemical deposition, is respectively necessary for different special
Industry instrument, causes preparation cost expensive, and, this kind of method the nuclear shell structure nano prepared
The carbon-coating on its surface of particle is relatively thin, and crystallinity is poor.
Summary of the invention
It is an object of the invention to, it is provided that one prepares onion-like fullerene cladding Metal Palladium nucleocapsid structure
The method of nanoparticle, it is capable of the preparation technology less demanding, one-tenth simply, to experiment condition
This is low, and can prepare the onion-like fullerene cladding Metal Palladium nucleocapsid structure of carbon-coating well-crystallized
Nanoparticle.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of prepare onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle method, including with
Lower step:
2,4-resorcylic acid and sodium hydroxide are dissolved in deionized water after being configured to solution and adding
Formaldehyde, stirs formation 2,4-resorcylic acid sodium-formalin, is subsequently adding sodium hydroxide pH value
Regulator regulation 2, the pH value of 4-resorcylic acid sodium-formalin, until becoming 2,4-dihydroxy
Yl benzoic acid sodium-formaldehyde colloidal sol；
By 2,4-resorcylic acid sodium-formaldehyde colloidal sol stands, thus obtains 2,4-resorcylic acid
Sodium-formaldehyde gel；
2,4-resorcylic acid sodium-formaldehyde gel is put into containing Pd2+Palladium salt solution in soak, enter
Row ion exchanges, and obtains being loaded with Pd2+2,4-resorcylic acid-formaldehyde gel；
Pd will be loaded with2+2,4-resorcylic acid-formaldehyde gel grind to form gel powder and at oxygen and
The mixed atmosphere of noble gas heats, when temperature rises to 950-1200 DEG C, at pure inert gas
Atmosphere in cool, obtain onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle.
Another object of the present invention is to, it is provided that a kind of onion-like fullerene cladding Metal Palladium nucleocapsid structure
Nanoparticle, its surface can form thicker carbon-coating structure, and carbon-coating crystallinity is good.
For achieving the above object, the onion-like fullerene cladding Metal Palladium nuclear shell structure nano grain of the present invention
Son is prepared from according to above-mentioned steps.And the onion-like fullerene cladding Metal Palladium core of the present invention
The concrete structure of shell structural nano particle be Metal Palladium nanoparticle be core, core outer cladding Bulbus Allii Cepae shape fowler
Alkene shell, shell has the thickness of 10-50nm.
The Advantageous Effects of the present invention:
The present invention becomes 2,4-bis-with 2,4-resorcylic acid, sodium hydroxide and formaldehyde for preparation of raw material
Hydroxy benzoic acid sodium-formalin, by 2,4-resorcylic acid sodium-formalin passes sequentially through and adds
Enter sodium hydroxide pH value regulator, stand step, it is thus achieved that 2,4-resorcylic acid sodium-formaldehyde coagulates
Glue, then by 2,4-resorcylic acid sodium-formaldehyde gel is put into containing Pd2+Palladium salt solution in soak
Bubble carries out ion exchange, thus obtains being loaded with Pd2+2,4-resorcylic acid-formaldehyde gel, so
After will be loaded with Pd2+2,4-resorcylic acid-formaldehyde gel grind to form gel powder and at oxygen and lazy
Property gas mixed atmosphere in heat, when temperature rises to 950-1200 DEG C, at pure inert gas
Atmosphere cools, thus obtains onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle.
The preparation technology of the present invention is simple, it is only necessary to be loaded with Pd by prepare2+2,4-resorcylic acid
-formaldehyde gel grind to form gel powder and in the mixed atmosphere of oxygen and noble gas reacting by heating, treat
After cooling, so that it may obtain onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle.Whole preparation
During, the requirement to experimental apparatus and reaction condition is the highest, it is not necessary to use expensive experiment to set
Standby or equipment, reduces preparation cost, and, the onion-like fullerene cladding Metal Palladium core of the present invention
Shell structural nano particle size is more uniform, and productivity is high, the carbon-coating well-crystallized of generation.
Accompanying drawing explanation
Fig. 1 is that the onion-like fullerene of preparing of the present invention is coated with Metal Palladium core-shell structure nanometer particle
Process chart；
Fig. 2 (a) is that the onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle of the present invention exists
The shape appearance figure observed under scanning electron microscope；
Fig. 2 (b) is that the onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle of the present invention exists
The local shape appearance figure observed under scanning electron microscope；
Fig. 3 (a) is that the onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle of the present invention exists
The structure chart of the shell observed under transmission electron microscope；
Fig. 3 (b) is that the onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle of the present invention exists
The structure chart of the shell observed under transmission electron microscope；
Fig. 3 (c) is that the onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle of the present invention exists
The structure chart of the nucleocapsid region observed under transmission electron microscope；
Fig. 3 (d) is the onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle of the present invention
Distribution diagram of element with the nucleocapsid region that electron energy filter stave is levied；
Fig. 4 (a) is that the Pd nano particle prepared in pure argon atmosphere is observed under scanning electron microscope
The shape appearance figure arrived；
Fig. 4 (b) is that the Pd nano particle prepared in pure argon atmosphere is observed under scanning electron microscope
The local shape appearance figure arrived；
Fig. 5 (a) is the palladium nanometer that oxygen concentration is prepared under conditions of being 0.5% in mixed atmosphere
The shape appearance figure that particle is observed under scanning electron microscope；
Fig. 5 (b) is the palladium nanometer that oxygen concentration is prepared under conditions of being 1.0% in mixed atmosphere
The shape appearance figure that particle is observed under scanning electron microscope；
Fig. 5 (c) is the palladium nanometer that oxygen concentration is prepared under conditions of being 1.5% in mixed atmosphere
The shape appearance figure that particle is observed under scanning electron microscope；
Fig. 5 (d) is the palladium nanometer that oxygen concentration is prepared under conditions of being 2.0% in mixed atmosphere
The shape appearance figure that particle is observed under scanning electron microscope；
Fig. 6 (a) is that the Pd nano particle prepared under conditions of heating-up temperature is 950 DEG C is at scanning electricity
The shape appearance figure that Microscopic observation arrives；
Fig. 6 (b) is that the Pd nano particle prepared under conditions of heating-up temperature is 850 DEG C is at scanning electricity
The shape appearance figure that Microscopic observation arrives；
Fig. 6 (c) is that the Pd nano particle prepared under conditions of heating-up temperature is 750 DEG C is at scanning electricity
The shape appearance figure that Microscopic observation arrives；
Fig. 6 (d) is that the Pd nano particle prepared under conditions of heating-up temperature is 650 DEG C is at scanning electricity
The shape appearance figure that Microscopic observation arrives；
Fig. 7 (a) is when temperature reaches 1050 DEG C, and the Pd nano particle after insulation 1h is at scanning electricity
The shape appearance figure that Microscopic observation arrives；
Fig. 7 (b) is when temperature reaches 1050 DEG C, and the Pd nano particle after insulation 2h is at scanning electricity
The shape appearance figure that Microscopic observation arrives；
Fig. 7 (c) is when temperature reaches 1050 DEG C, and the Pd nano particle after insulation 3h is at scanning electricity
The shape appearance figure that Microscopic observation arrives；
Fig. 8 (a) is to be to prepare under conditions of 17.5 DEG C/min is heated to 1050 DEG C with the rate of heat addition
The shape appearance figure observed under scanning electron microscope of Pd nano particle；
Fig. 8 (b) is to prepare under conditions of 9 DEG C/min is heated to 1050 DEG C with the rate of heat addition
The shape appearance figure that Pd nano particle is observed under scanning electron microscope；
Fig. 8 (c) is to prepare under conditions of 9 DEG C/min is heated to 1050 DEG C with the rate of heat addition
The shape appearance figure that Pd nano particle is observed under scanning electron microscope；
Fig. 9 is the growth of the onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle of the present invention
The schematic diagram of mechanism.
Detailed description of the invention
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but this area skill
Art personnel are it will be appreciated that the following example is merely to illustrate the present invention, and are not construed as limiting the present invention
Scope.Unreceipted actual conditions person in embodiment, the condition advised according to normal condition or manufacturer
Carry out.Agents useful for same or instrument unreceipted production firm person, being can be by commercially available purchase acquisition
Conventional products.
For ease of it will be appreciated by those skilled in the art that existing to some term related in the present invention or abridge into
Row explanation:
Sodium hydroxide pH value regulator: refer to for regulating 2,4-resorcylic acid sodium-formaldehyde molten
The sodium hydroxide solution of liquid pH value.Its solution concentration is the present invention be not particularly limited, art technology
Personnel can rationally select the sodium hydroxide solution of suitable concn according to practical situation.
Formaldehyde: the present invention uses general commercial formaldehyde, for liquid, concentration is about 38wt%.
DF:2,4-Dihydroxybenzoic acid-Formalin, 2,4-resorcylic acids-formaldehyde.
NPs:Nano Particles, nanoparticle.
CDF:Carbon-2,4-Dihydroxybenzoic acid-Formalin, the 2 of carbonization, 4-dihydroxy
Yl benzoic acid-formaldehyde
Pd-DF:Pd-2,4-Dihydroxybenzoic acid-Formalin is loaded with Pd2+2,4-dihydroxy
Yl benzoic acid-formaldehyde
The method bag preparing onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle of the present invention
Include following steps:
Step 1: preparation 2,4-resorcylic acid sodium-formaldehyde colloidal sol
By 2,4-resorcylic acid and sodium hydroxide are dissolved in deionized water and are configured to solution, then
Adding formaldehyde, stirring forms 2,4-resorcylic acid sodium-formalin；Add sodium hydroxide pH
Value regulator regulation 2, the pH value of 4-resorcylic acid sodium-formalin, until becoming 2,4-bis-
Hydroxy benzoic acid sodium-formaldehyde colloidal sol.
Preferably, by 2,4-resorcylic acid, sodium hydroxide and formaldehyde according to 1:1:4 mole
Than being configured to 2,4-resorcylic acid sodium-formalin, and regulated by sodium hydroxide pH value
Solution ph is regulated to 7-9 by agent, then dilutes with deionized water.
Step 2: preparation 2,4-resorcylic acid sodium-formaldehyde gel
By 2,4-resorcylic acid sodium-formaldehyde colloidal sol stands, thus obtains 2,4-resorcylic acid
Sodium-formaldehyde gel.
Preferably, 2,4-resorcylic acid sodium-formaldehyde colloidal sol stands 3-8 at a temperature of 50-70 DEG C
My god.Temperature height time of repose is short, and the low time of repose of temperature is long.The 2,4-dihydroxy benzenes first obtained
The density of acid sodium-formaldehyde gel is 0.1-0.3g/ml.
Step 3: preparation is loaded with Pd2+2,4-resorcylic acid-formaldehyde gel
2,4-resorcylic acid sodium-formaldehyde gel is put into containing Pd2+Palladium salt solution in soak, enter
Row ion exchanges, and obtains being loaded with Pd2+2,4-resorcylic acid-formaldehyde gel.
Preferably, by 2,4-resorcylic acid sodium-formaldehyde gel and containing Pd2+Palladium salt solution according to
The volume ratio of 1:4 soaks 20-30h, soaks 3-5 time.Containing Pd2+The density of palladium salt solution be
0.5-3g/L.Containing Pd2+Palladium salt solution e.g. PdCl2Solution, PdSO4Solution or Pd (NO3)2Molten
Liquid.
Step 4: prepare onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle
Pd will be loaded with2+2,4-resorcylic acid-formaldehyde gel grinds to form gel powder, by gel powder
The mixed atmosphere of oxygen and noble gas heats, when temperature rises to 950-1200 DEG C, pure
The atmosphere of noble gas cools, obtains onion-like fullerene cladding Metal Palladium nuclear shell structure nano
Particle.
Preferably, will grind after gel powder with the rate of heat addition for 5-20 DEG C/min in oxygen and inertia
The mixed atmosphere of gas is heated to 1000-1200 DEG C.Volume shared by oxygen in mixed atmosphere
Percentage ratio is 0.1%-0.5%.Noble gas e.g. helium, xenon or argon.
According to the method described above, the onion-like fullerene cladding Metal Palladium nucleocapsid structure preparing the present invention is received
Rice corpuscles.
Embodiment 1
According to the ratio that the mol ratio of 2,4-resorcylic acid, sodium hydroxide and formaldehyde is 1:1:4
Example prepare volume be 100mL, the 2 of density 0.1g/mL, 4-resorcylic acid sodium-formaldehyde gel,
Wherein, the density of 2,4-resorcylic acid sodium-formaldehyde gel is by 2, and 4-resorcylic acid sodium adds
The quality of upper formaldehyde obtains divided by the volume of 2,4-resorcylic acid sodium-formalin.
By 2,4-resorcylic acid 5.2g and sodium hydroxide 1.35g is first dissolved in deionized water, now
The volume of deionized water used, to be advisable less than 70mL, is configured to solution.2,4-dihydroxy benzenes first
Acid and sodium hydroxide react generation 2,4-resorcylic acid sodium, thus obtain 2,4-dihydroxy benzenes first
Acid sodium solution.
2,4-resorcylic acid sodium solution adds formalin 10mL that concentration is about 38wt%,
Stir, form light yellow transparent liquid.2,4-dihydroxy is regulated by sodium hydroxide pH value regulator
The pH value of yl benzoic acid sodium-formalin is to 7.Add deionized water, make total liquid volume arrive
100mL, stirs, and obtains 2,4-resorcylic acid sodium-formaldehyde colloidal sol.
2 will prepared, 4-resorcylic acid sodium-formaldehyde colloidal sol loads in hermetic container, at 50 DEG C
At a temperature of stand 8 days, formed brownish red clear gel, be 2,4-resorcylic acid sodium-first
Aldehyde gel.
Taking out 2,4-resorcylic acid sodium-formaldehyde gel, being cut into volume is 0.5-1cm3Fritter is put into
Density is 1.5g/L, volume is the PdSO of 400ml4Solution soaks 20h, carries out ion exchange, leaching
Steep 3 times, obtain being loaded with Pd2+2,4-resorcylic acid-formaldehyde gel.It is loaded with Pd2+2,4-
Resorcylic acid-formaldehyde gel is rufous, opaque gel.And this gel is at normal temperatures
For brittle substance, can directly pulverize.
Pd will be loaded with2+2,4-resorcylic acid-formaldehyde gel grind to form gel powder.By gel powder
The mixed atmosphere of oxygen and helium heats, and with the rate of heat addition of 10 DEG C/min, temperature is risen to
1000℃.Wherein, in mixed atmosphere, the concentration of oxygen is 0.1%.After temperature rises to 1000 DEG C,
By the natural cooling cooling in the atmosphere of pure helium of the powder after reacting by heating, i.e. obtain Bulbus Allii Cepae shape fowler
Alkene cladding Metal Palladium core-shell structure nanometer particle.
Embodiment 2
According to the ratio that the mol ratio of 2,4-resorcylic acid, sodium hydroxide and formaldehyde is 1:1:4
Example prepare volume be 100mL, the 2 of density 0.3g/mL, 4-resorcylic acid sodium-formaldehyde gel,
Wherein, the density of 2,4-resorcylic acid sodium-formaldehyde gel is by 2, and 4-resorcylic acid sodium adds
The quality of upper formaldehyde obtains divided by the volume of 2,4-resorcylic acid sodium-formalin.
By 2,4-resorcylic acid 15.6g and sodium hydroxide 4.06g is first dissolved in deionized water, this
The volume of Shi Suoyong deionized water, to be advisable less than 50mL, is configured to solution.2,4-dihydroxy benzenes
Formic acid and sodium hydroxide reaction generation 2,4-resorcylic acid sodium, thus obtain 2,4-dihydroxy benzenes
Sodium formate solution.
2,4-resorcylic acid sodium solution adds formalin 32mL that concentration is about 38wt%,
Stir, form light yellow transparent liquid.2,4-dihydroxy is regulated by sodium hydroxide pH value regulator
The pH value of yl benzoic acid sodium-formalin is to 9.Add deionized water, make total liquid volume arrive
100mL, stirs, and obtains 2,4-resorcylic acid sodium-formaldehyde colloidal sol.
2 will prepared, 4-resorcylic acid sodium-formaldehyde colloidal sol loads in hermetic container, at 70 DEG C
At a temperature of stand 3 days, formed brownish red clear gel, be 4-resorcylic acid sodium-formaldehyde
Gel.
Taking out 2,4-resorcylic acid sodium-formaldehyde gel, being cut into volume is 0.5-1cm3Fritter is put into
Density is 3g/L, volume is the PdCl of 400ml2Solution soaks 30h, carries out ion exchange, soak
5 times, obtain being loaded with Pd2+2,4-resorcylic acid-formaldehyde gel.It is loaded with Pd2+2,4-bis-
Hydroxy benzoic acid-formaldehyde gel is rufous, opaque gel.And this gel is at normal temperatures
Brittle substance, can directly pulverize.
Pd will be loaded with2+2,4-resorcylic acid-formaldehyde gel grind to form gel powder.By gel powder
The mixed atmosphere of oxygen and xenon heats, and with the rate of heat addition of 20 DEG C/min, temperature is risen to
1200℃.Wherein, in mixed atmosphere, the concentration of oxygen is 0.3%.After temperature rises to 1200 DEG C,
By the natural cooling cooling in the atmosphere of pure xenon of the powder after reacting by heating, i.e. obtain Bulbus Allii Cepae shape fowler
Alkene cladding Metal Palladium core-shell structure nanometer particle.
Embodiment 3
According to the ratio that the mol ratio of 2,4-resorcylic acid, sodium hydroxide and formaldehyde is 1:1:4
Example prepare volume be 100mL, the 2 of density 0.2g/mL, 4-resorcylic acid sodium-formaldehyde gel,
Wherein, the density of 2,4-resorcylic acid sodium-formaldehyde gel is by 2, and 4-resorcylic acid sodium adds
The quality of upper formaldehyde obtains divided by the volume of 2,4-resorcylic acid sodium-formalin.
By 2,4-resorcylic acid 8.0198g and sodium hydroxide 2.082g is first dissolved in deionized water,
The volume of deionized water the most used, to be advisable less than 70mL, is configured to solution.2,4-dihydroxy
Benzoic acid and sodium hydroxide reaction generation 2,4-resorcylic acid sodium, thus obtain 2,4-dihydroxy
PhCOONa solution.
The formalin that concentration is about 38wt% is added in 2,4-resorcylic acid sodium solution
15.43mL, stirs, and forms light yellow transparent liquid.Regulate by sodium hydroxide pH value regulator
The pH value of 2,4-resorcylic acid sodium-formalin is to 8.Add deionized water, make liquid total
Volume, to 100mL, stirs, and obtains 2,4-resorcylic acid sodium-formaldehyde colloidal sol.
2 will prepared, 4-resorcylic acid sodium-formaldehyde colloidal sol loads in hermetic container, at 60 DEG C
At a temperature of stand 7 days, formed brownish red clear gel, be 4-resorcylic acid sodium-formaldehyde
Gel.
Taking out 2,4-resorcylic acid sodium-formaldehyde gel, being cut into volume is 0.5-1cm3Fritter is put into
Density is 2g/L, volume is the PdCl of 400ml2Solution soaks 24h, carries out ion exchange, soak
4 times, obtain being loaded with Pd2+2,4-resorcylic acid-formaldehyde gel.It is loaded with Pd2+2,4-bis-
Hydroxy benzoic acid-formaldehyde gel is rufous, opaque gel.And this gel is at normal temperatures
Brittle substance, can directly pulverize.
Pd will be loaded with2+2,4-resorcylic acid-formaldehyde gel grind to form gel powder.By gel powder
The mixed atmosphere of oxygen and argon heats, and with the rate of heat addition of 17.5 DEG C/min by temperature liter
To 1050 DEG C.Wherein, in mixed atmosphere, the concentration of oxygen is 0.5%.When temperature rise to 1050 DEG C it
After, by the natural cooling cooling in the atmosphere of pure argon of the powder after reacting by heating, i.e. obtain Bulbus Allii Cepae shape
Fullerene cladding Metal Palladium core-shell structure nanometer particle.
Fig. 2 (a) is to the test result that Fig. 3 (d) is embodiment 3.
See Fig. 2 (a), sample creates a large amount of onion-like fullerene cladding Metal Palladium nucleocapsid structure
Nanoparticle, particle diameter is nanometer from tens of to hundreds of, and has some particles to flock together.Figure
2 (a) has not observed carbon skeleton.Fig. 2 (b) is the local after Fig. 2 (a) amplifies
Figure, from Fig. 2 (b) it will be clear that onion-like fullerene is coated with Metal Palladium nuclear shell structure nano
Particle has nucleocapsid structure, and shell is clear, and thickness is at about 10-50nm.
Seeing Fig. 3 (a) to Fig. 3 (d), the onion-like fullerene observed under transmission electron microscope is coated with
The nucleocapsid structure of Metal Palladium core-shell structure nanometer particle.By Fig. 3 (a) and Fig. 3 (b) it will be seen that
Outer shell lattice structure is in Bulbus Allii Cepae shape multiple structure clearly, and spacing of lattice is 0.33nm, Ke Yibiao
It is set to (002) crystal face of hexagonal phase carbon, coincide with the interlamellar spacing of graphite.See Fig. 3 (a), interior
The spacing of lattice of core is 0.21nm, is demarcated as (111) crystal face of Emission in Cubic palladium.This explanation nucleocapsid knot
Structure is Bulbus Allii Cepae shape orderly carbon-coating cladding Metal Palladium nanoparticle (Pd@C).
As shown in Fig. 3 (a) and Fig. 3 (b), the thickness of the multilamellar Fullerene Carbon shell of different particles
Differing, the carbon shell in Fig. 3 (a) only has about 10 layers, thickness about 4nm；In Fig. 3 (b)
The carbon shell of particle has 60 layers, and thickness is at least 20nm.
Meanwhile, it is observed that Metal Palladium kernel and carbon shell core-shell interface are clear from Fig. 3 (a)
Clear, it is completely embedded, lattice and the carbon lattice of palladium are directly connected to substantially, very close to each other.This explanation carbon is
Directly grow on palladium core surface.Further, do not observe the lattice of Palladium monoxide in interface, say
Bright reaction does not generate Palladium monoxide after completing.
For verifying that above-mentioned analysis, the present inventor compose (ELLS) with electron energy filter further
Characterize the Elemental redistribution in nucleocapsid structure region.The distribution diagram of element of Fig. 3 (d) illustrates intuitively
Pd@C nucleocapsid structure, wherein the scanning electron microscope (SEM) photograph of Pd and C element distribution shape and Fig. 3 (c) shows
Nucleocapsid structure basically identical, Pd element is mainly distributed on kernel, and C element constitutes outer shell.Wherein,
O element between palladium kernel and carbon shell is mainly derived from Pd nanoparticle outer layer in atmosphere
The oxygen of absorption.
Comparative example 1-4 is based on embodiment 3, and research different condition is rich to generating Bulbus Allii Cepae shape
Strangle the impact of alkene cladding Metal 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 benzenes
Formic acid-formaldehyde gel powder response situation under the conditions of oxygen-free atmosphere.Its result is as follows:
Seeing Fig. 4 (a) and Fig. 4 (b), it is the test result of comparative example.At pure argon gas
The sample of preparation under atmosphere, shown in its shape appearance figure under scanning electron microscope such as Fig. 4 (a), palladium nanoparticle
Son is distributed evenly in carbon skeleton.This explanation, when carrying out ion exchange, in Pd-DF gel,
Pd2+It is supported on equably on organic backbone.According to the local shape appearance figure shown by Fig. 4 (b), contrast
Not observing the Pd nano particle with nucleocapsid structure in the sample of embodiment, Pd nano particle is distributed in
On carbon skeleton.This illustrates, can not prepare and have nucleocapsid knot in the environment of pure argon (anaerobic)
The Pd nano particle of structure, in other words, oxygen has key to growth Pd@C core-shell structure nanometer particle
Effect.
Comparative experimental example 2
This test example have studied different oxygen concentration to generating onion-like fullerene cladding Metal Palladium nucleocapsid
The impact of structure nano particle.
See Fig. 5 (a) to Fig. 5 (d), under different oxygen concentrations, arrived by scanning electron microscope observation
The shape appearance figure of sample.The sample prepared when oxygen concentration 0.5% is mainly the nucleocapsid of carbon-coating cladding
Structured particles, as shown in Fig. 5 (a).Along with oxygen concentration increases to 1.0%, carbon back this reacted
, product is mainly the accumulation of palladium granule, does not observes and there is encasement layer outside particle, such as Fig. 5 (b)
Shown in.Oxygen concentration continues to increase, and to more than 1.5%, does not sees carbon, hence it is evident that observe palladium granule
Fusion is grown up, and forms stephanoporate framework, such as Fig. 5 (c) and Fig. 5 (d).
Therefore, in reaction atmosphere, oxygen concentration is very big on impacts such as product morphology structures, and oxygen concentration is not
Can be too high, it is advisable with 0.1%-0.5%.
Comparative experimental example 3
Originally test example and have studied different heating temperature to generating onion-like fullerene cladding Metal Palladium nucleocapsid knot
The impact of structure nanoparticle.
See Fig. 6 (a) to Fig. 6 (d), at different temperatures, the sample arrived by scanning electron microscope observation
The shape appearance figure of product.Fig. 6 (a) is the shape appearance figure under the conditions of 950 DEG C；Fig. 6 (b) is 850 DEG C of conditions
Under shape appearance figure；Fig. 6 (c) is the shape appearance figure under the conditions of 750 DEG C；Fig. 6 (d) is 650 DEG C of conditions
Under shape appearance figure.
It can be seen that 950 DEG C and following temperature cannot grow onion-like fullerene carbon coating layer.
At 950 DEG C of-750 DEG C of three temperature, the change of size of the Pd nano particle of synthesis is inconspicuous, around has carbon
Skeleton is isolated, and at 650 DEG C, carbon skeleton significant reaction is more, and palladium particle aggregation is grown up.This may
It is because carbon at 650 DEG C easily to cause with oxygen reaction.
Therefore, the heating-up temperature preparing onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle should
When more than 950 DEG C.
Comparative experimental example 4
Originally testing example and have studied when temperature is heated to 1050 DEG C, different temperature retention times are to generating Bulbus Allii Cepae shape
The impact of fullerene cladding Metal Palladium core-shell structure nanometer particle.
See Fig. 7 (a) to Fig. 7 (c), under different temperature retention times, arrived by scanning electron microscope observation
The shape appearance figure of sample.Fig. 7 (a) is the shape appearance figure of insulation 1h；Fig. 7 (b) is for insulation 2h's
Shape appearance figure；Fig. 7 (c) is the shape appearance figure of insulation 3h.
Under different temperature retention times, the sample of preparation all contains spherical Pd nano particle, and particle diameter is uneven
One.This explanation is in temperature-rise period, and particle has grown complete, does not substantially have during to insulation again
Growth, temperature retention time length is little on its impact.Therefore the preparation method of the present invention is incubated
Step.
Comparative experimental example 5
Originally test example and have studied different heating rates to generating onion-like fullerene cladding Metal Palladium nucleocapsid knot
The impact of structure nanoparticle.
See Fig. 8 (a) to Fig. 8 (c), under the rate of heat addition, the sample arrived by scanning electron microscope observation
The shape appearance figure of product.Fig. 8 (a) be with the rate of heat addition be 17.5 DEG C/min heating make temperature rise to 1050 DEG C
Shape appearance figure；Fig. 8 (b) and Fig. 8 (c) be the rate of heat addition be that 9 DEG C/min heating makes temperature rise to
The shape appearance figure of 1050 DEG C.
It can be seen that the fast sample of the rate of heat addition is substantially nucleocapsid structure particle, and when heating
Between long, the sample that the rate of heat addition is slow then has the shell carbon-coating of some particles react with oxygen, defines
The aggregate of palladium particle.
Based on above-mentioned test result, the present invention is prepared onion-like fullerene cladding Metal Palladium core by inventor
The method of shell structural nano particle provides following response mechanism, i.e. onion-like fullerene cladding Metal Palladium
The growth mechanism of core-shell structure nanometer particle.
See Fig. 9, in the ion exchange process of step 3, Pd2+Na is replaced by ion exchange+Negative
Being loaded in 2, in the skeleton of 4-resorcylic acid-formaldehyde gel, and be evenly distributed, this can be by anaerobic
Prepare Pd nano particle in sample (shown in Fig. 4 (b)) and be evenly distributed in carbon skeleton checking.
In step 4, to being loaded with Pd2+2,4-resorcylic acid-formaldehyde gel powder at oxygen and argon
Mixed atmosphere in heat, 2,4-resorcylic acids-formaldehyde gel molecular breakdown be organic molecule,
CO2、CH4、H2O etc..Owing to, during reacting by heating, reaction reproducibility is relatively strong, by C by Pd2+
It is reduced to Metal Palladium, assembles and be grown to Pd nano particle.In Pd nano particle surface and mixed atmosphere
Oxygen reaction, generates the oxidation state mixture of Pd.The oxide of Pd is the most stable, at high temperature
Generation simple substance Pd can be decomposed.Therefore when reaction temperature improves further, around Pd nano particle
C in organic molecule provides electronics, generates simple substance C；The peroxide breaks down of Pd simultaneously, accepts electricity
Son generates metal Pd.Thus, carbon, in Pd nano particle superficial growth, forms multilamellar fullerene cladding
Layer, is finally grown to serve as Pd@C nano particle.
If reaction is pure inert atmosphere, Pd nanoparticle surface will not form oxide layer, therefore anaerobic
Reaction will not be formed nucleocapsid structure particle.In oxidizing atmosphere, it is positioned at skeleton surface and neighbouring
Pd particle can touch oxygen, causes the growth of onion-like fullerene carbon-coating.
Although illustrate and describing the present invention with specific embodiment, but it will be appreciated that and do not carrying on the back
May be made that in the case of the spirit and scope of the present invention many other change and amendment.Therefore,
This means all these changes including belonging in the scope of the invention in the following claims and repair
Change.
Claims (10)
1. the method preparing onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle, its
It is characterised by, said method comprising the steps of:
2,4-resorcylic acid and sodium hydroxide are dissolved in deionized water after being configured to solution and adding
Formaldehyde, stirs formation 2,4-resorcylic acid sodium-formalin, is subsequently adding sodium hydroxide pH value
Regulator regulation described 2, the pH value of 4-resorcylic acid sodium-formalin, until becoming 2,4-
Resorcylic acid sodium-formaldehyde colloidal sol；
By described 2,4-resorcylic acid sodium-formaldehyde colloidal sol stands, thus obtains 2,4-dihydroxy benzenes
Sodium formate-formaldehyde gel；
Described 2,4-resorcylic acid sodium-formaldehyde gel is put into containing Pd2+Palladium salt solution in soak
Bubble, carries out ion exchange, obtains being loaded with Pd2+2,4-resorcylic acid-formaldehyde gel；
It is loaded with Pd by described2+2,4-resorcylic acid-formaldehyde gel grind to form gel powder and at oxygen
The mixed atmosphere of gas and noble gas heats, when temperature rises to 950-1200 DEG C, in pure inertia
The atmosphere of gas cools, obtains onion-like fullerene cladding Metal Palladium nuclear shell structure nano grain
Son.
Onion-like fullerene cladding Metal Palladium nucleocapsid structure of preparing the most according to claim 1 is received
The method of rice corpuscles, it is characterised in that by described 2,4-resorcylic acid, described sodium hydroxide
Become described 2,4-resorcylic acid sodium-formaldehyde molten with described formaldehyde according to the molar ratio of 1:1:4
Liquid, and add described sodium hydroxide pH value regulator by solution ph regulation to 7-9, then use
Deionized water dilutes.
Onion-like fullerene cladding Metal Palladium nucleocapsid structure of preparing the most according to claim 1 is received
The method of rice corpuscles, it is characterised in that described 2,4-resorcylic acid sodium-formaldehyde colloidal sol exists
3-8 days are stood at a temperature of 50-70 DEG C.
Onion-like fullerene cladding Metal Palladium nucleocapsid structure of preparing the most according to claim 1 is received
The method of rice corpuscles, it is characterised in that the density of described 2,4-resorcylic acid sodium-formaldehyde gel
For 0.1-0.3g/mL.
Onion-like fullerene cladding Metal Palladium nucleocapsid structure of preparing the most according to claim 1 is received
The method of rice corpuscles, it is characterised in that by described 2,4-resorcylic acid sodium-formaldehyde gel and institute
State containing Pd2+Palladium salt solution according to 1:4 volume ratio soak.
Onion-like fullerene cladding Metal Palladium nucleocapsid structure of preparing the most according to claim 5 is received
The method of rice corpuscles, it is characterised in that described 2,4-resorcylic acid sodium-formaldehyde gel puts into institute
State containing Pd2+Palladium salt solution in soak 3-5 time, soak 20-30h every time.
Onion-like fullerene cladding Metal Palladium nucleocapsid structure of preparing the most according to claim 5 is received
The method of rice corpuscles, it is characterised in that described containing Pd2+The density of palladium salt solution be 0.5-3g/L.
Onion-like fullerene cladding Metal Palladium nucleocapsid structure of preparing the most according to claim 1 is received
The method of rice corpuscles, it is characterised in that the described gel powder after grinding is at oxygen and noble gas
Being heated to 950-1200 DEG C in mixed atmosphere, the rate of heat addition is 5-20 DEG C/min.
Onion-like fullerene cladding Metal Palladium nucleocapsid structure of preparing the most according to claim 8 is received
The method of rice corpuscles, it is characterised in that in described mixed atmosphere, the percent by volume shared by oxygen is
0.1%-0.5%.
10. an onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle, it is characterised in that
Described nanoparticle is to be coated with gold according to the onion-like fullerene of preparing one of claim 1 to 9 Suo Shu
Prepared by the method for genus palladium core-shell structure nanometer particle.
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| CN106621962A (en) * | 2017-01-04 | 2017-05-10 | 太原理工大学 | Method for dispersing carbon onion |
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