CN106916110A - A kind of carried noble metal nano composition and preparation method thereof - Google Patents
A kind of carried noble metal nano composition and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of carried noble metal nano composition and preparation method thereof, more particularly to a kind of stable chemical performance metal organic framework supported precious metal nano-particle composite and preparation method thereof.The uniform particle diameter of the noble metal nano particles in composite of the invention, and narrow distribution range, in 3~4nm.The present invention is sour as presoma using inorganic noble metal, by selecting stable chemical nature, carrier will not be used as by the metal organic framework that inorganic noble metal aqueous acid corrodes in preparation process, and the method for combining specific wet impregnation+in-situ reducing, obtain composite of the invention.Quick, mild condition not only simple to operate of the invention, the exposure crystal face that can also control the noble metal nano particles in the compound for obtaining is face-centered cubic fcc (111) crystal face, is had a extensive future.
Description
Technical field
The invention belongs to nano-particle preparation field, it is related to a kind of carried noble metal nano composition and its system
Preparation Method, more particularly to a kind of metal organic framework supported precious metal nano-particle composite, and with stable chemical nature
Metal organic framework for carrier, inorganic noble metal acid for presoma, using dipping quickly and easily made with reference to local reduction way
The method of standby composite.
Background technology
Metal organic framework (Metal Organic Frameworks, MOF) be a kind of high-specific surface area, it is ordered porous,
There is the metallo-organic framework material of certain chemistry and heat endurance, ground extensively in recent years as a kind of novel material
Study carefully, it is the fields such as separation, energy storage, administration, catalysis that it is mainly applied.Wherein, ZIF-67 is used as a kind of zeolite type MOF, due to it
The good characteristic of MOF and zeolite is combined, in materials synthesis field by extensive concern.
In terms of synthesis is with MOF as carrier loaded various metal nanoparticles, people have been achieved for very big progress.People
Explored a variety of synthetic methods and synthesized such material, in conventional document, the MOF carried noble metal nanoparticles of report
The method of son it is usually used be organic precious metal forerunner costly, and local reduction way used is hydrogen hot conditions
Lower reduction.Also need to add stabilizer in sectional interest.These methods prepare cumbersome and high cost, severe reaction conditions, and
Metal nanoparticle generally existing homogeneity in the product for obtaining is poor, particle size distribution range is too wide and nano-particle between roll into a ball
Poly- problem.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of carried noble metal nanometer
Particle composite material and preparation method thereof.The method of the present invention can make the noble metal nano particles stable and uniform such as Pd, Pt and Au
Be distributed on metal organic framework, and keep very narrow particle diameter distribution, less particle diameter (3nm~4nm) and monodispersity.And
And, the method for the present invention is simple to operate, quick, mild condition, can also realize controlling the noble metal in the compound for obtaining to receive
The exposure crystal face of rice corpuscles is face-centered cubic fcc (111) crystal face.
In a first aspect, the present invention provides a kind of carried noble metal nano composition, the carried noble metal
Nano composition includes carrier and the noble metal nano particles being supported on carrier, wherein, the carrier is metal
Organic backbone, in metal organic framework supported on carriers stabilization, particle diameter is smaller and homogeneous, and particle diameter is equal for the noble metal nano particles
Between 3nm~4nm, distribution is narrower.
In composite of the invention, the particle diameter of noble metal nano particles in 3nm~4nm, for example, 3nm, 3.1nm,
Specific point value between 3.2nm, 3.3nm, 3.4nm, 3.5nm, 3.7nm or 4nm etc., and above-mentioned numerical value, as space is limited and goes out
In concise consideration, the present invention specific point value that no longer scope described in exclusive list includes.
Preferably, the noble metal nano particles are in homogeneous single dispersing state.
As the optimal technical scheme of carried noble metal nano composition of the present invention, the composite
In noble metal nano particles inorganic noble metal aqueous acid is reduced using reducing agent, it is described reduction it is excellent
Elect in-situ reducing as.
In the present invention, described " inorganic noble metal acid " refers to：Inorganic acid comprising precious metal element, for example, gold chloride,
The acid of chlorine palladium and chloroplatinic acid etc..
In present invention, it is desirable to ensureing during reduction, metal organic framework is in inorganic noble metal aqueous acid
Stabilization, does not corrode.
Present invention preferably employs metal organic framework be ZIF-67.ZIF-67 is a kind of zeolite type metal organic framework,
It has excellent chemical stability and heat endurance, during preparing composite for the present invention, will not be by inorganic expensive
Metal aqueous acid corrodes, Stability Analysis of Structures.
Preferably, combination of the noble metal nano particles including any one in Pd, Pt or Au or at least two, but
The above-mentioned material enumerated is not limited to, other noble metal nano particles commonly used in the art can also be used for the present invention.
Your preferably, counted by 100wt% of the gross mass of the carried noble metal nano composition, the gold
Belong to nano-particle weight/mass percentage composition be 3.3wt%~10.2wt%, for example, 3.3wt%, 3.5wt%, 3.7wt%,
4.0wt%, 4.5wt%, 4.75wt%, 5.0wt%, 5.5wt%, 6.0wt%, 6.3wt%, 6.6wt%, 7.0wt%,
7.5wt%, 8.0wt%, 8.5wt%, 9.0wt%, 9.5wt% or 10.0wt% etc..
Used as the optimal technical scheme of carried noble metal nano composition of the present invention, the present invention provides one
Plant ZIF-67 supported precious metal nano-particle composites.In the composite, noble metal nano grain of the particle diameter in 3nm~4nm
Son stabilization and equably using single dispersing state be supported on ZIF-67 as carrier on.
Second aspect, the present invention provides the preparation of carried noble metal nano composition as described in relation to the first aspect
Method, the described method comprises the following steps：
(1) inorganic noble metal aqueous acid is prepared；
(2) inorganic noble metal aqueous acid is added in the suspension of the metal organic framework of purple and is impregnated；
(3) dissolve reduce agent in solvent, the dispersion liquid that then will be obtained is added to the leaching obtained after step (2) dipping
In stain system, stirring, system color is changed into black, obtains carried noble metal nano composition from purple.
Preferably, in step (1) the inorganic noble metal aqueous acid, the molar concentration of inorganic noble metal acid is 35mM
~70mM, preferably 50mM.
Preferably, the inorganic noble metal acid includes any one in the acid of chlorine palladium, chloroplatinic acid or gold chloride or at least two
The combination planted, but the above-mentioned inorganic noble metal acid enumerated is not limited to, other inorganic noble metals acid commonly used in the art also can use
In the present invention.
In the method for the present invention, in the inorganic noble metal aqueous acid of step (2) and the suspension of metal organic framework
Metal organic framework do not corrode, it is therefore an objective to guarantee to obtain by metal organic framework carrier and load on this carrier
Noble metal nano particles constitute composite, preferred metal organic framework be ZIF-67 and/or ZIF-8, it is especially excellent
Elect ZIF-67 as.
" ZIF-67 and/or ZIF-8 " of the present invention refers to：Can be ZIF-67, or ZIF-8, can also be
The mixture of ZIF-67 and ZIF-8.
Preferably, the suspension of step (2) described metal organic framework is molten by the way that metal organic framework powder is dissolved in
Obtained in agent.
Preferably, the metal organic framework powder relative to solvent mass-volume concentration (15~20) mg/10mL, example
Such as it is 15mg/10mL, 16mg/10mL, 18mg/10mL, 19mg/10mL or 20mg/10mL, preferably 20mg/10mL.
Preferably, during the suspension of preparation steps (2) described metal organic framework, the solvent be water and/or
Organic solvent, preferably organic solvent, more preferably methyl alcohol.
Preferably, it is described super also with ultrasound during the suspension of preparation steps (2) described metal organic framework
The time of sound is preferably 5min~20min, for example, 5min, 6min, 8min, 10min, 13min, 15min or 20min etc., enters
One step is preferably 10min.
Preferably, the volume ratio of the suspension of step (2) the inorganic noble metal aqueous acid and metal organic framework
It is 1:100~1:20, for example, 1:100、1:90、1:80、1:70、1:60、1:55、1:50、1:40、1:300 or 1:20 etc..
Preferably, the mode of step (2) described addition is preferably slowly added dropwise to be added dropwise.
Preferably, the speed of the dropwise addition be 30 drop it is per minute~60 drop it is per minute.
Preferably, 3h~8h is preferably with stirring, the time of stirring during step (2) described dipping, for example,
3h, 4h, 5h, 6h, 7h or 8h etc., preferably 6h.
Preferably, combination of step (3) the described reducing agent including any one in sodium borohydride or hydrazine hydrate or two kinds,
But the above-mentioned material enumerated is not limited to, other reducing agents commonly used in the art can also be used for the present invention.
Preferably, step (3) described solvent is water and/or organic solvent, preferably organic solvent, more preferably first
Alcohol, the methyl alcohol for particularly preferably cooling down.
Preferably, with ultrasound during step (3) dissolves reduce agent in solvent, the time of the ultrasound is preferably
10s~30s, preferably 10s.
Preferably, in step (3), the reducing agent is (3~10) 1mg/ relative to the mass-volume concentration of the solvent
ML, for example, 3mg/1mL, 3.5mg/1mL, 4mg/1mL, 4.2mg/1mL, 4.6mg/1mL, 5mg/1mL, 5.3mg/1mL,
5.5mg/1mL, 6mg/1mL, 6.5mg/1mL, 7mg/1mL, 7.5mg/1mL, 8mg/1mL, 8.5mg/1mL, 9mg/1mL or
10mg/1mL etc., preferably 7.2mg/1mL.
Preferably, the volume ratio of the dipping system that step (3) dispersion liquid is obtained after being impregnated with step (2) is
1.05:1~1.30:1, for example, 1.05:1、1.10:1、1.15:1、1.20:1、1.23:1、1.25:1、1.28:1 or 1.30:1
Deng.
Preferably, the time of step (3) described stirring is 0.5h~2h, for example, 0.5h, 1h, 1.2h, 1.5h or 2h etc.,
Preferably 1h.
Used as the optimal technical scheme of the method for the invention, methods described is additionally included in step (3) stirring and completes laggard
The step that row is separated, washs and dried.
Separation of the present invention can use separation means commonly used in the prior art, such as filter or be centrifuged, preferably from
The heart simultaneously obtains clear liquid.
Preferably, the rotating speed of the centrifugation is 600rpm~1000rpm, preferably 8000rpm.
Preferably, the time of the centrifugation is 10min.
Preferably, the number of times of the washing is 3 times.
Preferably, the drying is carried out under the conditions of lucifuge；
Preferably, the dry temperature is room temperature, preferably 25 DEG C.
" room temperature " of the present invention refers to 20 DEG C~30 DEG C, for example, 20 DEG C, 22 DEG C, 24 DEG C, 25 DEG C, 26 DEG C, 27 DEG C or 30
DEG C etc..
Preferably, the dry time be preferably 12h.
Compared with the prior art, the present invention has the advantages that：
(1) the invention provides a kind of noble metal nano particles by metal organic framework carrier and load on this carrier
The composite of composition, the noble metal nano particles particle diameter in the composite is small, and narrow distribution range, 2nm~
4nm, and the noble metal nano particles such as palladium, platinum and gold and metal organic framework carrier combination stabilization, good dispersion shows
Extraordinary single dispersing state.
(2) the invention provides a kind of simple, quick and leniently prepare carried noble metal nano composition
Method, it uses the acid of inorganic noble metal as presoma, using stable chemical performance, will not be by inorganic expensive in preparation process
The metal organic framework of metal aqueous acid corrosion has synthesized this hair as carrier by wet impregnation+in-situ reducing technology
Bright composite, the exposure crystal face that can control the noble metal nano particles in the compound for obtaining is face-centered cubic fcc
(111) crystal face.
(3) present invention prepares carried noble metal nano composition from the acid of inorganic noble metal as presoma,
Compared to conventional organic precursor, have the advantages that it is cheap be easy to get, and preparation method of the invention it is simple, quick,
Mild condition, easily realizes industrialized production.
Brief description of the drawings
Fig. 1 is the transmission electron microscope photo of the ZIF-67 supported palladium nano compositions prepared by the embodiment of the present invention 1.
Fig. 2 is the high-resolution transmission electricity of the ZIF-67 supported palladium nano compositions prepared by the embodiment of the present invention 1
Mirror photo.
Fig. 3 is the transmission electron microscope photo of the ZIF-67 supported platinum nano particle composite materials prepared by the embodiment of the present invention 2.
Fig. 4 is the high-resolution transmission electricity of the ZIF-67 supported platinum nano particle composite materials prepared by the embodiment of the present invention 2
Mirror photo.
Fig. 5 is the transmission electron microscope photo of the ZIF-67 load gold nano particle composite materials prepared by the embodiment of the present invention 3.
Fig. 6 is the high-resolution transmission electricity of the ZIF-67 load gold nano particle composite materials prepared by the embodiment of the present invention 3
Mirror photo.
Fig. 7 is the transmission electron microscope photo of the ZIF-8 supported palladium nano compositions prepared by the embodiment of the present invention 4.
Fig. 8 is the high-resolution-ration transmission electric-lens of the ZIF-8 supported palladium nano compositions prepared by the embodiment of the present invention 4
Photo.
Specific embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by specific embodiment.
Embodiment 1
First, according to document (Li, H.；Ma,H.；Wang,X.；Gao,J.；Chen,C.；Shi,S.；Qu,M.；Feng,
N.；Xu, J.Journal of Energy Chemistry 2014,23,742) prepare ZIF-67.Weigh 20mg ZIF-67
Powder, is dissolved in 10ml methyl alcohol, ultrasonic dissolution 10min, obtains the suspended liquid system of purple.Configure the chlorine palladium aqueous acid of 50mM.
The 300 μ L chlorine palladium aqueous acids are pipetted with pipettor, ZIF-67 methanol solutions system (i.e. above-mentioned purple suspension is slowly dropped into
System) in, 6h is stirred, to complete dipping process.The sodium borohydride of 7.2mg is weighed, is dissolved in the methyl alcohol of 1ml coolings, ultrasound is molten
Solution 10s, the dispersion liquid that will be obtained is added in the dipping system that above-mentioned dipping is completed, and system is changed into black from purple.Persistently stir
1h is mixed, then with 8000rpm centrifugation 10min, clear liquid is separated, is cleaned repeatedly with methyl alcohol 3 times.Sample lucifuge at room temperature
12h is dried, ZIF-67 supported palladium nano compositions are obtained, ZIF-67@Pd NP are named as.
Products therefrom ZIF-67 supported palladium nano compositions are entered using transmission electron microscope and high-resolution-ration transmission electric-lens
Row phenetic analysis, referring to Fig. 1, high-resolution-ration transmission electric-lens photo is referring to Fig. 2 for transmission electron microscope photo.
Found from characterization result, the acid of chlorine palladium is by being changed into Pd nano particle of the growth in situ on ZIF-67 after reduction.
From in terms of the result that the transmission electron microscope of Fig. 1 is characterized, the Pd nano particle dispersiveness being supported on ZIF-67 is very good, and particle diameter distribution
Homogeneous, particle diameter is 3.5nm ± 0.5nm (wherein ± 0.5nm represents the deviation of statistics)；From the high-resolution-ration transmission electric-lens result of Fig. 2
See, the exposure crystal face of Pd nano particle, interplanar distance can be controlled as carrier and with reference to the method for the present invention using ZIF-67
It is 0.23nm, fcc (111) crystal face of correspondence palladium.
Embodiment 2
ZIF-67 is prepared using method same as Example 1.20mg ZIF-67 powder is weighed, 10ml methyl alcohol is dissolved in
In, ultrasonic dissolution 10min obtains the suspended liquid system of purple.Configure the chloroplatinic acid aqueous solution of 50mM.300 μ L are pipetted with pipettor
The chloroplatinic acid aqueous solution, is slowly dropped into ZIF-67 methanol solutions system (the suspended liquid system of i.e. above-mentioned purple), stirs 6h, with
Complete dipping process.The sodium borohydride of 7.2mg is weighed, is dissolved in the methyl alcohol of 1ml coolings, ultrasonic dissolution 10s, the dispersion that will be obtained
Liquid is added in the dipping system that above-mentioned dipping is completed, and system is changed into black from purple.1h is persistently stirred, then with 8000rpm
Centrifugation 10min, separates clear liquid, is cleaned repeatedly with methyl alcohol 3 times.Lucifuge dries 12h to sample at room temperature, obtains ZIF-67
Supported platinum nano particle composite material, is named as ZIF-67@Pt NP.
Products therefrom ZIF-67 supported platinum nano particle composite materials are entered using transmission electron microscope and high-resolution-ration transmission electric-lens
Row phenetic analysis, referring to Fig. 3, high-resolution-ration transmission electric-lens photo is referring to Fig. 4 for transmission electron microscope photo.
Find that chloroplatinic acid is by being changed into nano platinum particle of the growth in situ on ZIF-67 after reduction from characterization result.
From in terms of the result that the transmission electron microscope of Fig. 3 is characterized, the nano platinum particle dispersiveness being supported on ZIF-67 is very good, and particle diameter distribution
Homogeneous, particle diameter is 3.3nm ± 0.5nm (wherein ± 0.5nm represents the deviation of statistics)；From the high-resolution-ration transmission electric-lens result of Fig. 4
See, ZIF-67 can control the exposure crystal face of nano platinum particle as carrier, interplanar distance is 0.23nm, the fcc of correspondence platinum
(111) crystal face.
Embodiment 3
First, ZIF-67 is prepared using method same as Example 1.20mg ZIF-67 powder is weighed, 10ml is dissolved in
In methyl alcohol, ultrasonic dissolution 10min obtains the suspended liquid system of purple.Configure the aqueous solution of chloraurate of 50mM.Pipetted with pipettor
The 300 μ L aqueous solution of chloraurate, are slowly dropped into ZIF-67 methanol solutions system (the suspended liquid system of i.e. above-mentioned purple), stir
6h, to complete dipping process.The sodium borohydride of 7.2mg is weighed, is dissolved in the methyl alcohol of 1ml coolings, ultrasonic dissolution 10s will be obtained
Dispersion liquid be added in the dipping system that above-mentioned dipping is completed, system is changed into black from purple.Persistently stir 1h, then with
8000rpm centrifugation 10min, separate clear liquid, are cleaned repeatedly with methyl alcohol 3 times.Lucifuge dries 12h to sample at room temperature, obtains
ZIF-67 load gold nano particle composite materials are obtained, ZIF-67@Au NP are named as.
Products therefrom ZIF-67 load gold nano particle composite materials are entered using transmission electron microscope and high-resolution-ration transmission electric-lens
Row phenetic analysis, referring to Fig. 5, high-resolution-ration transmission electric-lens photo is referring to Fig. 6 for transmission electron microscope photo.
Find that gold chloride is by being changed into golden nanometer particle of the growth in situ on ZIF-67 after reduction from characterization result.
From in terms of the result that the transmission electron microscope of Fig. 1 is characterized, the golden nanometer particle dispersiveness being supported on ZIF-67 is very good, and particle diameter distribution
Homogeneous, particle diameter is 3.3nm ± 0.5nm (wherein ± 0.5nm represents the deviation of statistics)；From the high-resolution-ration transmission electric-lens result of Fig. 2
See, ZIF-67 can control the exposure crystal face of golden nanometer particle as carrier, interplanar distance is 0.23nm, the fcc of correspondence gold
(111) crystal face.
Embodiment 4
First, according to document (Torad, N.L.；Hu,M.；Kamachi,Y.；Takai,K.；Imura,M.；Naito,M.；
Yamauchi, Y.Chemical communications 2013,49,2521) prepare ZIF-8.Weigh 20mg ZIF-8 powder
End, is dissolved in 10ml methyl alcohol, ultrasonic dissolution 15min, obtains milky white suspended liquid system.Configure the chlorine palladium aqueous acid of 50mM.With
Pipettor pipettes the 500 μ L chlorine palladium aqueous acids, is slowly dropped into ZIF-67 methanol solutions system (i.e. above-mentioned milky suspension
System) in, 6h is stirred, to complete dipping process, obtain yellowish color system.The sodium borohydride of 10mg is weighed, 1ml coolings are dissolved in
In methyl alcohol, ultrasonic dissolution 10s, the dispersion liquid that will be obtained is added in the dipping system that above-mentioned dipping is completed, and system is by faint yellow
It is changed into black.1h is persistently stirred, then with 6000rpm centrifugation 10min, clear liquid is separated, is cleaned repeatedly with methyl alcohol 3 times.Sample
Lucifuge dries 12h to product at room temperature, obtains ZIF-8 supported palladium nano compositions, is named as ZIF-8@Pd NP.
Products therefrom ZIF-8 supported palladiums nano composition is carried out using transmission electron microscope and high-resolution-ration transmission electric-lens
Phenetic analysis, referring to Fig. 7, high-resolution-ration transmission electric-lens photo is referring to Fig. 8 for transmission electron microscope photo.
Found from characterization result, the acid of chlorine palladium is by being changed into Pd nano particle of the growth in situ on ZIF-8 after reduction.From
The result that the transmission electron microscope of Fig. 7 is characterized sees that the Pd nano particle dispersiveness being supported on ZIF-8 is very good, and particle diameter distribution is equal
One, particle diameter is 3.3nm ± 0.5nm (wherein ± 0.5nm represents the deviation of statistics)；From in terms of the high-resolution-ration transmission electric-lens result of Fig. 8,
The exposure crystal face of Pd nano particle can be controlled as carrier and with reference to the method for the present invention using ZIF-8, interplanar distance is
0.23nm, fcc (111) crystal face of correspondence palladium.
Embodiment 5
First, ZIF-67 is prepared using method same as Example 1.15mg ZIF-67 powder is weighed, 10ml is dissolved in
In methyl alcohol, ultrasonic dissolution 10min obtains the suspended liquid system of purple.Configure the aqueous solution of chloraurate of 60mM.Pipetted with pipettor
The 300 μ L aqueous solution of chloraurate, 60 drops speed per minute instills ZIF-67 methanol solutions system (i.e. above-mentioned purple suspension
System) in, 3h is stirred, it is added in the dipping system that above-mentioned dipping is completed with the dispersion liquid for completing, system is changed into black from purple
Color.Persistently stir dipping process.The sodium borohydride of 7.2mg is weighed, is dissolved in the methyl alcohol of 2ml coolings, ultrasonic dissolution 10s, will
To 2h, with 8000rpm centrifugation 6min, clear liquid is separated, cleaned repeatedly with methyl alcohol 3 times.Lucifuge is dried sample at room temperature
12h, obtains ZIF-67 load gold nano particle composite materials, is named as ZIF-67@Au NP.
Product to the present embodiment is characterized, and is found from result, and gold chloride exists by being changed into growth in situ after reduction
Golden nanometer particle on ZIF-67.From in terms of the result that transmission electron microscope is characterized, the golden nanometer particle dispersiveness on ZIF-67 is supported on
It is very good, and particle diameter distribution is homogeneous, particle diameter is 3.3nm ± 0.5nm (wherein ± 0.5nm represents the deviation of statistics)；From high-resolution
Transmission electron microscope results see that ZIF-67 can control the exposure crystal face of golden nanometer particle as carrier, and interplanar distance is 0.23nm, right
Fcc (111) crystal face of Ying Jin.
Comparative example 1
In addition to ZIF-67 is replaced with into MOF-525, other preparation methods and condition are same as Example 2.
In the preparation process of this comparative example, after adding inorganic noble metal acid, MOF-525 is decomposed immediately, thus cannot be obtained
MOF-525 supported platinum nano particle composite materials.
Comparative example 2
In addition to being proceeded as follows after completing dipping process, other preparation methods and condition are same as Example 2, described
Operate and be：Lucifuge under the presoma room temperature (20 DEG C to 30 DEG C of scope) for completing dipping is dried into 12h, is placed in magnetic boat, be put into pipe
In formula stove, heated up with 5 to 10 DEG C/min, 3h is heated at 230 DEG C, be passed through 10% hydrogen of volume fraction/helium, flow control exists
5ml/min。
The product that this comparative example is prepared is characterized, is as a result found, the noble metal of the load of gained is all reunited
Seriously, it is impossible to obtain nano-particle.
Applicant states that the present invention illustrates method detailed of the invention by above-described embodiment, but the present invention not office
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of carried noble metal nano composition, it is characterised in that the carried noble metal nano-particle is answered
Condensation material includes carrier and load noble metal nano particles on the carrier；
Wherein, the carrier be metal organic framework, the uniform particle diameter of the noble metal nano particles, particle diameter is in 3nm~4nm.
2. carried noble metal nano composition according to claim 1, it is characterised in that the noble metal is received
Rice corpuscles is in single dispersing state.
3. carried noble metal nano composition according to claim 1 and 2, it is characterised in that your gold
Category nano-particle is reduced using reducing agent to inorganic noble metal aqueous acid, and the reduction is preferably original position
Reduction；
Preferably, metal organic framework stabilization in the inorganic noble metal aqueous acid, and do not corrode；
Preferably, the metal organic framework is ZIF-67.
4. the carried noble metal nano composition according to claim any one of 1-3, it is characterised in that described
Combination of the noble metal nano particles including any one in Pd, Pt or Au or at least two.
5. the carried noble metal nano composition according to claim any one of 1-4, it is characterised in that with institute
The gross mass of carried noble metal nano composition is stated for 100wt% is counted, the quality hundred of the noble metal nano particles
Content is divided to be 3.3wt%~10.2wt%.
6. the preparation method of the carried noble metal nano composition as described in claim any one of 1-5, its feature
It is that the described method comprises the following steps：
(1) inorganic noble metal aqueous acid is prepared；
(2) inorganic noble metal aqueous acid is added in the suspension of metal organic framework and is impregnated；
(3) dissolve reduce agent in solvent, the dispersion liquid that then will be obtained is added to the impregnating obtained after step (2) dipping
In system, stirring obtains carried noble metal nano composition.
7. method according to claim 6, it is characterised in that in step (1) the inorganic noble metal aqueous acid, nothing
The molar concentration of machine noble metal acid is 35mM~70mM, preferably 50mM；
Preferably, the inorganic noble metal acid includes any one in the acid of chlorine palladium, chloroplatinic acid or gold chloride or at least two
Combination；
Preferably, step (2) the inorganic noble metal aqueous acid is to the metal in the suspension of the metal organic framework
Organic backbone does not corrode, and the metal organic framework is preferably ZIF-67 and/or ZIF8, more preferably ZIF-67；
Preferably, the suspension of step (2) described metal organic framework is dissolved in solvent by by metal organic framework powder
Obtain；
Preferably, the metal organic framework powder is (15~20) mg/10mL relative to the mass-volume concentration of solvent, preferably
It is 20mg/10mL；
Preferably, during the suspension of preparation steps (2) described metal organic framework, the solvent is water and/or organic
Solvent, preferably organic solvent, more preferably methyl alcohol；
Preferably, during the suspension of preparation steps (2) described metal organic framework, also with ultrasound, the ultrasound
Time is preferably 5min~20min, more preferably 10min；
Preferably, step (2) the inorganic noble metal aqueous acid and the volume ratio of the suspension of metal organic framework are 1:
100~1:20；
Preferably, the mode of step (2) described addition is to be added dropwise, the speed of dropwise addition be preferably 30 drops it is per minute~60 every point of drops
Clock；
Preferably, 3h~8h, preferably 6h are preferably with stirring, the time of stirring during step (2) described dipping.
8. the method according to claim 6 or 7, it is characterised in that step (3) described reducing agent includes sodium borohydride or water
Close the combination of any one or two kinds in hydrazine；
Preferably, step (3) described solvent is water and/or organic solvent, preferably organic solvent, more preferably methyl alcohol,
The methyl alcohol for particularly preferably cooling down；
Preferably, with ultrasound during step (3) dissolves reduce agent in solvent, it is described ultrasound time be preferably 10s~
30s, preferably 10s；
Preferably, in step (3), the reducing agent is (3~10) 1mg/mL relative to the mass-volume concentration of the solvent, excellent
Elect 7.2mg/1mL as；
Preferably, the volume ratio of the dipping system that step (3) dispersion liquid is obtained after being impregnated with step (2) is 1.05:1~
1.30:1；
Preferably, the time of step (3) described stirring is 0.5h~2h, preferably 1h.
9. the method according to claim any one of 6-8, it is characterised in that it is described that methods described is additionally included in step (3)
The step for being separated after the completion of stirring, being washed and being dried.
10. method according to claim 9, it is characterised in that the mode of the separation is：It is centrifuged and isolated clear
Liquid；
Preferably, the rotating speed of the centrifugation is 600rpm~1000rpm, preferably 8000rpm；
Preferably, the time of the centrifugation is 10min；
Preferably, the number of times of the washing is 3 times；
Preferably, the drying is carried out under the conditions of lucifuge；
Preferably, the dry temperature is 20 DEG C~30 DEG C, preferably 25 DEG C；
Preferably, the dry time be preferably 12h.
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