CN104607652B - Controllable precious metal nanocatalyst synthesis method with amino acid as soft templates - Google Patents
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Abstract
The invention relates to the field of precious metal nanocatalyst preparation, and discloses a preparation method for regulating and controlling the structure and morphology of precious metal nanocatalyst with amino acid as soft templates. According to the method, precious metal salt serves as precursors, polyvinylpyrrolidone (PVP) and amino acid serve as dispersion agents and the soft templates respectively, and the amino-acid-oriented precious metal nanocatalyst is constructed through a hydrothermal route. By regulating the type and addition amount of amino acid, hexahedral, branch-shaped and chain-shaped precious metal nanoparticles with the controllable morphology and sizes can be obtained, and the high reproducibility is achieved. Due to the fact that amino acid is rich in resource and low in price, the preparation method is economical, easy and suitable for industrial large-scale production, and has good application prospects in the field of heterogeneous catalysis and electric catalysis.
Description
Technical field
The present invention relates to a kind of noble metal nano method for preparing catalyst, and in particular to one kind is by the use of aminoacid as soft mode
Plate is regulating and controlling the preparation method of noble metal nano catalyst structure and pattern.
Background technology
Fuel cell（Including alcohols, acids and Ammonia fuel cell etc.）Chemical energy can be converted directly into electric energy, be had
The advantages of energy conversion efficiency is high, pollution is little, fuel is diversified, is generally acknowledged efficient, green energy conversion technology, always with
To be considered automobile, portable or fixed power source system potential energy source device.
Due to " geometric effect " and " crystal face effect ", the noble metal nano catalyst with specific morphology and size is
Cause extensive concern in Industrial Catalysis and fuel cell field.A kind of important method for improving electrocatalysis characteristic is exactly to noble metal
Nanocatalyst pattern and surface high preferred orientation are controlled.Platinum（Pt）And palladium（Pd）As noble metal be research in it is most commonly seen
Two kinds of catalyst, its crystal plane structure all be face-centered cubic (fcc) structure.In previously studying, crystal face control has been had proven to right
Electro catalytic activity and selective importance.For example, with regard to fuel battery negative pole oxygen reduction reaction（ORR）, the low index of three kinds of Pt
Crystal face corresponding electro catalytic activity in sulfuric acid medium is Pt (110)> Pt(100)>Pt(111)；And for ammonia oxidation
(NOR) react, electro catalytic activity is Pt (100)> Pt(111) >Pt(110).Therefore, the controllable conjunction of noble metal nano catalyst
One of the focus studied in the always field and difficult point.
At present, the Pt and Pd noble metal catalyst of different-shape, such as nanometer tetrahedron, nanometer octahedron, nanosphere, nanometer
Line, nano-hollow ball and nanocube, with different synthetic methods（Including template, crystal seed method, chemical reduction method,
Sol-gel process and thermal decomposition method）Prepare.In these synthetic methods, functional molecular (protective agent, stabilizer, surface
Activating agent, additive etc.) there is important function to the synthesis of the morphology control of noble metal nano particles, especially in wet chemistry method
In shape controlled synthesis.Conventional functional molecular has ascorbic acid, carbon monoxide, cetyl trimethylammonium bromide, hexadecane
Base trimethyl ammonium chloride etc..However, these functional moleculars can produce certain Toxic during noble metal nano particles are prepared
Matter, is unfavorable for building the synthesis theory of environmental protection.
The content of the invention
It is an object of the invention to provide one kind is by the use of aminoacid as soft template controlledly synthesis noble metal nano catalyst
Method, i.e., using aminoacid, noble metal salt, polyvinylpyrrolidone（PVP）For raw material, by simple hydrothermal reduction method
Noble metal nanometer material is prepared, described method can regulate and control nanoparticle pattern and size, and gained nanocatalyst can be used for
Fuel-cell catalyst, meets relevant field application and the requirement for developing.
The present invention is adopted the following technical scheme that：It is a kind of to be catalyzed as soft template controlledly synthesis noble metal nano by the use of aminoacid
The method of agent, in deionized water, forms aminoacid and water-soluble precious metal salt ultrasonic mixing aminoacid-precious metal salt and coordinates
Thing；Subsequently by polyvinylpyrrolidone（PVP）In being added to aminoacid-precious metal salt complex solution, adjust solution ph to
OK range；Directly above-mentioned solution is put in hydrothermal reaction kettle, or formaldehyde is added in above-mentioned solution（HCHO）Solution is obtained
Reaction system, in being then placed in hydrothermal reaction kettle, reaction at a certain temperature is completely reduced noble metal salt, product point
From, wash, be drying to obtain described noble metal nano catalyst.
More specifically, the side by the use of aminoacid as soft template controlledly synthesis noble metal nano catalyst of the invention
Method, comprises the following steps：
（1）Synthesizing amino acid-precious metal salt coordination compound：In deionized water, by aminoacid and water-soluble precious metal salt with
Certain ratio ultrasonic mixing forms aminoacid-precious metal salt coordination compound；
（2）By polyvinylpyrrolidone（PVP）In being added to aminoacid-precious metal salt complex solution, pH value of solution is adjusted
It is worth to OK range；
（3）Precious metal salt is reduced：Directly by above-mentioned steps（2）Resulting solution is put in hydrothermal reaction kettle, or to above-mentioned step
Suddenly（2）Formalin is added in resulting solution, in being subsequently placed into hydrothermal reaction kettle；By reactor as the drying under uniform temperature
Reaction in case is completely reduced noble metal salt；
（4）Post processing：By step（3）After gained black suspension thing centrifugation, washing, vacuum drying is obtained final product described
Noble metal nano catalyst.
In said method, aminoacid is used as functional molecular（Soft template）Controllable Pt, Pd noble metal nano catalyst structure
And pattern, PVP plays a part of stabilizer in nanoparticle building-up process, and can preferably be regulated and controled by changing pH value
The reduction potential of precious metal salt.The controllable hexahedron of appearance and size, branched and chain can be obtained using said method expensive
Metal nanoparticle.
The preferred Palladous chloride. of described precious metal salt（PdCl2）And potassium chloroplatinite（K2PtCl4）Deng.
Described aminoacid includes but is not limited to lysine and arginine etc..
Lysine arginine
Described aminoacid is 2 with the molar ratio of precious metal salt：1~10：1.
The OK range of described mixed solution pH value is 3.0 ~ 12.0.
Described polyvinylpyrrolidone preferred molecular weight 30000.The preferred 40%wt of concentration of described HCHO.
Described reaction temperature is preferably 140oC～160oC, the response time is preferably 4 hours.
The present invention is one kind by the use of aminoacid as functional molecular（Soft template）To regulate and control Pt, Pd noble metal nano catalyst
The method of structure and pattern, described method can be expensive with the hexahedron of controlledly synthesis different-shape size, branched and chain
Metal nanoparticle.Protein is the bioactive molecule in human nutrition, and aminoacid, as the main constituents of protein, is egg
The basis of white matter molecular activity, thus the preferable biocompatibility of aminoacid, beneficial to the synthesis theory for building environmental protection.Together
When, the amino energy and Pt in aminoacidII、PdII、AuIII、CoII、NiII、CuIIAnd AgIReact to each other generation aminoacid-MxCoordinate
Thing (Mx=PtII、PdII、AuIII、CoII、NiII、CuIIAnd AgI), and then significantly reduce MxThe reduction potential and reduction speed of presoma
Rate, makes to be possibly realized by controlling kinetics regulation and control nanoparticle pattern；Further, since strong aminoacid-MxCoordinate
Effect, aminoacid noble metal nano particles surface adsorption can cause nanoparticle combine can strong change (i.e. electronics knot
The change of structure), and then the electro catalytic activity of noble metal nano particles is regulated and controled by electronic effect.
It is an advantage of the current invention that：The present invention adopts abundance, and aminoacid cheap and easy to get is as functional molecular to expensive
Metal nanoparticle pattern is regulated and controled, and by the type and addition that adjust aminoacid, can obtain appearance and size controllable
Hexahedron, branched and chain noble metal nano particles, with higher repeatability.Because origin of amino acid enriches, price
Cheap, the preparation method economy of the present invention, simple for process, suitable industrialization large-scale production are urged in incorgruous catalysis and electricity
Change field has good application prospect.Specifically include：
（1）The formation of amino acid molecular and noble metal salt coordination compound, thus it is possible to vary the reduction potential of noble metal salt,
So as to play a part of to regulate and control nanoparticle pattern and size；
（2）By the type and addition that adjust aminoacid, the controllable of different-shape noble metal nano particles can be realized
Synthesis.Meanwhile, the uniform particle diameter of nanoparticle, dispersibility and good stability；
（3）Aminoacid is environmentally friendly biomolecule, with preferable biocompatibility；
（4）Preparation method is simple, economical, is adapted to industrial mass production.
Description of the drawings
Fig. 1 schemes for the TEM of hexahedron shape Pt nanoparticles obtained in the embodiment of the present invention 1；
Fig. 2 schemes for the TEM of branch-like Pd nanoparticle obtained in the embodiment of the present invention 2；
Fig. 3 schemes for the TEM of chain Pd nanoparticles obtained in the embodiment of the present invention 4；
Fig. 4 schemes for the TEM of self assembly chain Pd nanoparticles obtained in the embodiment of the present invention 3；
Fig. 5 schemes for the SEM of self assembly chain Pd nanoparticles obtained in the embodiment of the present invention 3.
Specific embodiment
Describe the present invention with reference to specific embodiment.Protection scope of the present invention is not being embodied as
Mode is limited, but is defined in the claims.
Embodiment 1
It is a kind of by the use of aminoacid as the method for soft template controlledly synthesis noble metal nano catalyst, comprise the following steps：
（1）Pipette the M lysine solutions of 0.5 ml 0. 5 and the M K of 1.0 ml 0.052PtCl4Solution is added to 8 ml
In deionized water, ultrasonic mixing forms uniform lysine-K2PtCl4Complex solution；
（2）Under stirring to lysine-K2PtCl450 mg polyvinylpyrrolidones are added in complex solution
（PVP）, adjust mixed solution pH to 9.0；
（3）To step（2）Mixed solution in add 0.5 ml HCHO (40%wt) solution, be subsequently placed into hydro-thermal reaction
In kettle；Reactor is placed in 160 DEG C of drying baker and reacts 4 h；
（4）After gained black suspension thing centrifugation, washing, vacuum drying obtains final product the Pt of the lysine controlledly synthesis
Nanoparticle.
The TEM of the Pt nanoparticles of above-mentioned preparation is observed, as shown in Figure 1, Pt nanoparticles are to be uniformly dispersed, size is equal
One hexahedron pattern.
Embodiment 2
It is a kind of by the use of aminoacid as the method for soft template controlledly synthesis noble metal nano catalyst, comprise the following steps：
（1）Pipette the M arginine solution of 0.4 ml 0. 5 and the M PdCl of 0.5 ml 0.052Solution is added to 8 ml and goes
In ionized water, ultrasonic mixing forms uniform arginine-PdCl2Complex solution；
（2）Under stirring to arginine-PdCl250 mg polyvinylpyrrolidones are added in complex solution
（PVP）, adjust mixed solution pH to 12.0；
（3）To step（2）Mixed solution in add 0.5 ml HCHO (40%) solution, be subsequently placed into hydrothermal reaction kettle
In；Reactor is placed in 140 DEG C of drying baker and reacts 4 h；
（4）After gained black suspension thing centrifugation, washing, vacuum drying obtains final product the Pd of the arginine controlledly synthesis
Nanoparticle.
The TEM of the Pd nanoparticles of above-mentioned preparation is observed, as shown in Figure 2, Pd nanoparticles are finely dispersed four-footed
Branch-like pattern.
Embodiment 3
It is a kind of by the use of aminoacid as the method for soft template controlledly synthesis noble metal nano catalyst, comprise the following steps：
（1）Pipette the M lysine solutions of 0.4 ml 0. 5 and the M PdCl of 0.5 ml 0.052Solution is added to 8 ml and goes
In ionized water, ultrasonic mixing forms uniform lysine-PdCl2Complex solution；
（2）Under stirring to lysine-PdCl250 mg polyvinylpyrrolidones are added in complex solution
（PVP）, adjust mixed solution pH to 12.0；
（3）Subsequently by step（2）Mixed solution be put in hydrothermal reaction kettle（Note：Exist without HCHO in this example）, will
It is placed in 140 DEG C of drying baker and reacts 2 h；
（4）After gained black suspension thing centrifugation, washing, vacuum drying obtains final product the Pd of the lysine controlledly synthesis
Nanoparticle.
The TEM figures of the Pd nanoparticles of above-mentioned preparation are observed, as shown in Figure 3, Pd nanoparticles are chain pattern.
Embodiment 4
It is a kind of by the use of aminoacid as the method for soft template controlledly synthesis noble metal nano catalyst, comprise the following steps：
（1）Pipette the M arginine solution of 0.4 ml 0. 5 and the M PdCl of 0.5 ml 0.052Solution is added to 8 ml and goes
In ionized water, ultrasonic mixing forms uniform arginine-PdCl2Complex solution；
（2）Under stirring to arginine-PdCl250 mg polyvinylpyrrolidones are added in complex solution
（PVP）, adjust mixed solution pH to 12.0；
（3）Subsequently by step（2）Mixed solution be put in hydrothermal reaction kettle（Note：Exist without HCHO in this example）, will
It is placed in 140 DEG C of drying baker and reacts 2 h；
（4）After gained black suspension thing centrifugation, washing, vacuum drying obtains final product the Pd of the arginine controlledly synthesis
Nanoparticle.
The TEM and SEM figure of the Pd nanoparticles of above-mentioned preparation is observed, as shown in Figure 4, Pd nanoparticles are chain knot
Structure, examines and we have found that chain structure is that have single small size Pd self-assembly to form.
Above-described embodiment has been described in detail to technical scheme, it should be understood that the above
Specific embodiment only of the invention, is not limited to the present invention, it is all done in the spirit of the present invention any repair
Change or improve, should be included within the scope of the invention.
Claims (5)
1. a kind of method by the use of aminoacid as soft template controlledly synthesis noble metal nano catalyst, it is characterised in that described
Method is in deionized water, aminoacid and water-soluble precious metal salt ultrasonic mixing to be formed into aminoacid-precious metal salt and is coordinated
Thing, described aminoacid and the molar ratio of precious metal salt is 2：1~10：1；Subsequently by polyvinyl pyrrole that molecular weight is 30000
Alkanone is added in aminoacid-precious metal salt complex solution, adjusts solution ph to 3.0 ~ 12.0 scopes；Directly will be above-mentioned molten
Liquid is put in hydrothermal reaction kettle, or adds formalin to obtain reaction system in above-mentioned solution, is then placed in hydrothermal reaction kettle
In, reaction at a certain temperature is completely reduced noble metal salt, and product is separated, washed, being drying to obtain described noble metal
Nanocatalyst.
2. the method by the use of aminoacid as soft template controlledly synthesis noble metal nano catalyst according to claim 1,
Characterized in that, described method is comprised the following steps：
（1）Synthesizing amino acid-precious metal salt coordination compound：In deionized water, by aminoacid with water-soluble precious metal salt with certain
Ratio ultrasonic mixing formed aminoacid-precious metal salt coordination compound；
（2）Polyvinylpyrrolidone is added in aminoacid-precious metal salt complex solution, solution ph is adjusted to suitable model
Enclose；
（3）Precious metal salt is reduced：Directly by above-mentioned steps（2）Resulting solution is put in hydrothermal reaction kettle, or to above-mentioned steps（2）
Formalin is added in resulting solution, in being subsequently placed into hydrothermal reaction kettle；By reactor as in the drying baker under uniform temperature
Reaction is completely reduced noble metal salt；
（4）Post processing：By step（3）After gained black suspension thing centrifugation, washing, vacuum drying obtains final product your described gold
Category nanocatalyst.
3. the side by the use of aminoacid as soft template controlledly synthesis noble metal nano catalyst according to claim 1 and 2
Method, it is characterised in that described precious metal salt is PdCl2Or K2PtCl4。
4. the side by the use of aminoacid as soft template controlledly synthesis noble metal nano catalyst according to claim 1 and 2
Method, it is characterised in that described aminoacid is lysine or arginine.
5. the side by the use of aminoacid as soft template controlledly synthesis noble metal nano catalyst according to claim 1 and 2
Method, it is characterised in that described reaction temperature is 120oC～180oC, the response time is 2 hours～8 hours.
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| CN108465825A (en) * | 2018-04-25 | 2018-08-31 | 常州市蓝勖化工有限公司 | A kind of preparation method of the special dispersed nano copper powder of lube oil additive |
| CN110368998B (en) * | 2019-07-11 | 2022-04-08 | 东南大学 | Core-shell structure nano composite material based on biological method and preparation method thereof |
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