CN105149611B - A kind of hollow noble metal nano wire and its preparation and application - Google Patents
A kind of hollow noble metal nano wire and its preparation and application Download PDFInfo
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- CN105149611B CN105149611B CN201510599913.4A CN201510599913A CN105149611B CN 105149611 B CN105149611 B CN 105149611B CN 201510599913 A CN201510599913 A CN 201510599913A CN 105149611 B CN105149611 B CN 105149611B
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Abstract
The present invention relates to a kind of hollow noble metal nano wire and its preparation and application.This method makees reducing agent using ascorbic acid, and Pt or Rh and Ag salt are reduced into metallic atom；Protective agent is made with diallyl dimethyl ammoniumchloride, template-mediated that nano material grows acted on by it, at room temperature the hollow nano wires of one-step synthesis M Ag.Meanwhile, Pt Ag or Pd Ag nanowire surfaces are coated on protective agent, the stability and water solubility of Pt Ag or Pd Ag nano wires can be greatly improved, are to be laid the first stone in the future in biological field and catalytic field application.The hollow nano wires of M Ag are prepared using this method, technique is simple, Product yields are high, even structure is controllable, and short preparation period, be easy to quick, substantial amounts of prepare.The inventive method preparation condition is easily controlled, and required equipment is simple, and it is higher that product is prepared into power, with good prospects for commercial application.
Description
Technical field
The invention belongs to noble metal nanometer material technical field, it is related to a kind of hollow noble metal nano wire and its preparation and answers
With.
Background technology
Noble metal nanometer material has important application prospect in fields such as catalysis, electronics, optics.Wherein, the expensive gold of Pt bases
Category nano-particle due to being received significant attention with good catalytic activity (C.Cui, L.Gan, H.H.Li, S.H.Yu,
M.Heggen,P.Strasser.Nano Lett.2012,12,5885-5889).The catalytic activity of noble metal nanometer material is not only
Dependent on particle size, but also depending on the shape of material, the Nomenclature Composition and Structure of Complexes.It is double due to intermetallic synergic catalytic effect
Metal nano material shows more excellent performance, thus cause Domestic Scientific Research worker attention (L.Liu,
E.Pippel.Angew.Chem.Int.Ed.,2010,50,1–6).In addition, hollow noble metal nanometer material is due to big
Specific surface area, also show good application prospect in catalytic field.It is inferred that many metal hollow nano materials are likely to
Have better performance.At present, the synthesis of many metal one-dimensional hollow nano materials is mainly reacted by Galvanic, usually with active
Metal nanometer line or nanometer rods do template, by Pt or Pd ions and its generation displacement reaction, obtain hollow many metal nanos
Line (L.Liu, E.Pippel.Angew.Chem.Int.Ed., 2010,50,1-6).This method usually needs two steps to carry out, i.e.,
The first step synthesizes Ag monodimension nanometer materials, and second step carries out Galvanic reaction, and this preparation method preparation process is comparatively laborious.
Therefore, the technical problem that presently, there are is that to need to research and develop a kind of preparation process relatively simple and urged with higher
Change noble metal nano wire catalyst of activity and preparation method thereof.
The content of the invention
The technical problems to be solved by the invention are that there is provided a kind of hollow noble metal nano in view of the shortcomings of the prior art
Line, the hollow noble metal nano wire has higher catalytic activity, and preparation method is simple, short preparation period, is easy to quick, big
The preparation of amount.
Therefore, the invention provides a kind of hollow noble metal nano wire, it is the hollow nano wires of M-Ag, wherein, M and Ag's
Mol ratio is (0.1-10):1；It is preferred that M and Ag mol ratio (1-5):1；The M is Pt or Pd.
Present invention also offers a kind of preparation method of above-mentioned hollow noble metal nano wire, it is included to protective agent-solvent
M metal precursors, AgNO are added in mixed liquor3And reducing agent, carry out reacting obtained noble metal nano wire again after being well mixed.
According to the present invention, M metal precursors and AgNO3Mol ratio be (0.1-10):1；It is preferred that M metal precursors with
AgNO3Mol ratio be (1-5):1.The mol ratio of ascorbic acid and M metal precursors is 5:1.
In the present invention, the M metal precursors include at least one of Pt salt, Pt acid and Pd salt；The Pt acid H2PtCl6；
The Pt salt is Na2PtCl6And/or K2PtCl；The Pd salt is K2PdCl4And/or Na2PdCl4。
In a preferred embodiment of the invention, the temperature of the reaction is 25 DEG C；The reaction time is 15-
20hr；It is preferred that the time of the reaction is 20hr.
It is protectant water-soluble in the protective agent-solvent mixed liquor in another preferred embodiment of the present invention
The volume ratio of liquid and solvent is 1:50.
According to the present invention, in protectant aqueous solution, protectant mass concentration is 20% to 35%；Institute
Protective agent is stated for diallyl dimethyl ammoniumchloride.
According to the present invention, the solvent is polyalcohol, and it is included in ethylene glycol, glycerine, pentanediol and diethylene glycol extremely
Few one kind；Preferred polyol includes at least one of ethylene glycol, glycerine and pentanediol.
In the present invention, preferably described reducing agent is ascorbic acid.
The present invention still further provides one kind according to above-mentioned hollow noble metal nano wire as catalyst in electro-catalysis first
Application in alcohol oxidation reaction.
Brief description of the drawings
Illustrate the present invention below in conjunction with accompanying drawing.
Fig. 1 is the transmission electron microscope photo of synthesized hollow Pt-Ag nano wires in embodiment 1.
Fig. 2 is the transmission electron microscope photo of synthesized hollow Pd-Ag nano wires in embodiment 4.
Fig. 3 is the active Electrochemical results of sign nanowire catalytic；Wherein, short-term type dotted line is in embodiment 7
Pt and Ag mol ratios are 1:1 nano wire is used for the result that catalysis methanol is aoxidized；Point line style dotted line is Pt and Ag in embodiment 6
Mol ratio is 5:1 nano wire is used for the result that catalysis methanol is aoxidized；Solid line is business Pt catalysis methanol oxidation results.
Embodiment
To make the present invention easier to understand, the present invention is described in detail below in conjunction with embodiment and accompanying drawing, these realities
Apply example and only play illustrative effect, it is not limited to application of the invention.
As it was previously stated, the preparation process for preparing noble metal nano wire catalyst is more complicated.
Therefore, one aspect of the present invention is related to a kind of hollow noble metal nano wire, its be the hollow nano wires of M-Ag, wherein, M with
Ag mol ratio is (0.1-10):1；It is preferred that M and Ag mol ratio (1-5):1；The M is Pt or Pd.
In the present invention, the metal M-Ag for constituting the above-mentioned hollow nano wires of M-Ag is actually the M-Ag of alloying, i.e. alloy
The Pt-Ag or Pd-Ag of change.
Another aspect of the present invention is related to a kind of preparation method of above-mentioned hollow noble metal nano wire, it include to protective agent-
M metal precursors, AgNO are added in solvent mixed liquor3And reducing agent, carry out reacting obtained noble metal nano again after being well mixed
Line.
The method that the present invention prepares hollow noble metal nano wire is to utilize co-reducing process, reduced using ascorbic acid
Agent, the hollow Pt-Ag and Pd-Ag nano wires of one-step synthesis.
The present invention has investigated the influence that different metal salt in the preparation process of hollow noble metal nano wire is cooked presoma, finds
Metal salt provided by the present invention may be incorporated for growing the hollow nano wires of M-Ag.
In certain embodiments of the present invention, M metal precursors and AgNO3Mol ratio be (0.1-10):1；It is preferred that M
Metal precursor and AgNO3Mol ratio be (1-5):1；The mol ratio of ascorbic acid and M metal precursors is 5:1.
In other embodiments of the present invention, the M metal precursors are included at least one in Pt salt, Pt acid and Pd salt
Kind；The Pt acid is H2PtCl6；The Pt salt is Na2PtCl6And/or K2PtCl；The Pd salt is K2PdCl4And/or
Na2PdCl4。
In the present invention, preferably M metal precursors carry out drying process using preceding.
The present invention has investigated reaction temperature and reaction time in the preparation process of hollow noble metal nano wire and nano wire has been given birth to
Long influence, finds just generate hollow noble metal nano wire under room temperature condition, and the reaction time product structure is influenceed compared with
Greatly.
According to certain embodiments of the present invention, the temperature of the reaction is 25 DEG C.The reaction time is 15-20hr；
It is preferred that the time of the reaction is 20hr.
The present inventor's research is found, during hollow noble metal nano wire is prepared, with polydiene propyl group two
Ammonio methacrylate makees protective agent, and template-mediated that nano material grows is acted on by it, Pt or Rh and Ag salt are reduced to
Metallic atom, so as to be grown to serve as one-dimensional hollow Nano line.Further, during hollow noble metal nano wire is prepared,
With protective agent, such as diallyl dimethyl ammoniumchloride is coated on Pt-Ag or Pd-Ag nanowire surfaces, can greatly improve
The stability and water solubility of Pt-Ag or Pd-Ag nano wires, are to be laid the first stone in the future in biological field and catalytic field application.
The present invention has investigated various concentrations protective agent, such as polydiene propyl group in the preparation process of hollow noble metal nano wire
The influence that alkyl dimethyl ammonium chloride grows to hollow noble metal nano wire, it is found that proper amount of protective agent is conducive to growth M-Ag hollow
Nano wire.Meanwhile, different molecular weight polydiene propyl group two in the preparation process of the invention for also having investigated hollow noble metal nano wire
Ammonio methacrylate does protectant influence, it is found that different molecular weight diallyl dimethyl ammoniumchloride can serve as protective agent
For growing the hollow nano wires of M-Ag；Wherein, using diallyl dimethyl ammoniumchloride that molecular weight is 200,000-100 ten thousand as most
It is good.
According to the inventive method, in the protective agent-solvent mixed liquor, the volume ratio of the protectant aqueous solution and solvent
For 1:50.
In certain embodiments of the present invention, in protectant aqueous solution, protectant mass concentration
For 20% to 35%；The protective agent includes but is not limited to diallyl dimethyl ammoniumchloride.
In the present invention, the molecular weight of preferably described diallyl dimethyl ammoniumchloride is 20 ten thousand to 100 ten thousand.
The present inventor also studies discovery, due to chloroplatinic acid and diallyl dimethyl ammoniumchloride in course of reaction
Cl ions are introduced, so that the Ag ions introduced with silver nitrate are had an effect, AgCl are generated；And using polyalcohol as solvent and protective agent
It is engaged, is conducive to AgCl and H2PtCl6The structure of some wire is formed, these linear structures, which can be used as template, to be used to form sky
Core structure.
In the present invention, the solvent is polyalcohol, and it is included in ethylene glycol, glycerine, pentanediol and diethylene glycol at least
It is a kind of；Preferred polyol is selected from least one of ethylene glycol, glycerine and pentanediol.
In the present invention, the reducing agent is ascorbic acid.
The present invention has investigated different polyalcohols in the preparation process of hollow noble metal nano wire and has made solvent to hollow noble metal
The influence of nanowire growth, it is found that above-mentioned polyalcohol may be used to grow the hollow nano wires of M-Ag.Wherein, with ethylene glycol, third
Triol or pentanediol are most beneficial for the growth hollow nano wires of M-Ag.
In a word, at room temperature, under the protective agent effect of suitable concn, it can be easy to prepare hollow Pt-Ag and Pd-Ag receives
Rice noodles.
The present invention is further directed to one kind and (is referred to as according to above-mentioned hollow noble metal nano wire as catalyst in the present invention
Hollow noble metal nano wire catalyst) application in electro-catalysis methanol oxidation.
Through experiment, hollow noble metal nano wire of the invention in electro-catalysis methanol oxidation there is higher catalysis to live
Property, it is potential fuel battery anode catalyst.
In some preferred embodiments of the present invention, methods described is additionally included in after obtained hollow noble metal nano wire
Centrifugal treating is repeated in hollow noble metal nano wire and the step of obtaining pure hollow noble metal nano wire is washed.
In a preferred embodiment of the invention, in above-mentioned steps, centrifugal treating rotating speed is 10000 revs/min.
In another preferred embodiment of the invention, in above-mentioned steps, preferably washed by solvent of deionized water
Wash.
In the specific embodiment of the present invention, the hollow nano wire of M-Ag of the invention is made using following steps
It is standby：
The diallyl dimethyl ammoniumchloride of 20mL polyalcohols and 0.4mL finite concentrations and molecular weight is mixed equal
It is even, the dried M metal precursors of addition and AgNO3(M metal precursors and AgNO3Mol ratio be (0.1-10):1).
After mixed liquor stirs, adding ascorbic acid, (mol ratio of ascorbic acid and M metal precursors is 5:1), in certain temperature
Lower stirring 20h, obtains the hollow nano wires of one-dimensional M-Ag.
Described polyalcohol is at least one of ethylene glycol, glycerine, pentanediol and diethylene glycol；Preferred polyol is selected from
At least one of ethylene glycol, glycerine and pentanediol.
Described diallyl dimethyl ammoniumchloride molecular weight is 20 ten thousand to 100 ten thousand.
Described diallyl dimethyl ammoniumchloride mass concentration is 20% to 35%.
The M metal precursors include at least one of Pt salt, Pt acid and Pd salt；The Pt acid H2PtCl6；The Pt salt
For Na2PtCl6And/or K2PtCl；The Pd salt is K2PdCl4And/or Na2PdCl4。
Described reaction temperature is room temperature (25 DEG C).
The pure hollow nano wires of M-Ag are dispersed on the copper mesh for being loaded with carbon film, with transmission electron microscope observation, it is tied
Structure.
The method that the hollow nano thread structures of M-Ag are observed in the present invention：The pure hollow nano wires of M-Ag are dispersed in and are loaded with
On the copper mesh of carbon film, observed with transmission electron microscope (JEOL 2100F, Jeol Ltd.) and grow front-end geometry
Change.
In the present invention, the characterizing method of nanowire catalytic activity is：
By the nano wire sample of preparation by centrifuging (10000 revs/min) collections, then it is scattered in again in 50mL distilled water
And centrifuge again, three removings of said process excessive protective agent and solvent are repeated, is then dispersed in 20mL water, passes through ultrasound
It is uniformly dispersed within 30 minutes, takes 20 microlitres to drip on glass-carbon electrode, removes the organic matter on surface after drying by ion etching.
Resulting hollow nano wire is tested as electrode for methanol oxidation, as a result M-Ag of the invention is hollow receives
Rice noodles are shown with the activity higher than commercial catalysts.
The present invention utilizes co-reducing process, and reducing agent is made using ascorbic acid, and Pt or Rh and Ag salt are reduced into metal raw
Son；Protective agent is made with diallyl dimethyl ammoniumchloride simultaneously, template-mediated that nano material grows is acted on by it, made
Obtain M-Ag and be grown to serve as one-dimensional hollow Nano line, so that the hollow nano wires of the one-dimensional M-Ag of one-step synthesis at room temperature.Further,
During hollow noble metal nano wire is prepared, with protective agent, such as diallyl dimethyl ammoniumchloride is coated on Pt-Ag
Or Pd-Ag nanowire surfaces, the stability and water solubility of Pt-Ag or Pd-Ag nano wires can be greatly improved, is in the future in biology
Field and catalytic field application lay the first stone.
Compared with traditional noble metal catalyst, the hollow nano wires of one-dimensional M-Ag, technique letter are prepared using the inventive method
Single, Product yields are high, even structure is controllable, and short preparation period, are easy to quick, substantial amounts of prepare.The inventive method preparation side
The condition of method is easily controlled, and required equipment is simple, and it is higher that product is prepared into power, with good prospects for commercial application.
Embodiment
Embodiment 1：Use H2PtCl6Do Pt sources and prepare hollow Pt-Ag nano wires (Pt and Ag mol ratios are 0.12).
At normal temperatures, 2.9mg H are taken2PtCl6With 10mg AgNO3It is dissolved in 20mL ethylene glycol, adds 15mg Vitamin Cs
Acid, adds 0.4mL diallyl dimethyl ammoniumchlorides, after ultrasonic dissolution is complete, and arrest reaction 20h, obtains ash at room temperature
The hollow Pt-Ag nano wires of brown.Reaction solution in bottle is moved on in centrifuge tube, 10 minutes (10000 revs/min), precipitum are centrifuged
It is dispersed in water again, then centrifugal sedimentation again, repeats sedimentation and centrifugal process 3 times, removes accessory substance in solution and many
Remaining solvent and protective agent, finally can obtain pure hollow Pt-Ag nano wires.
Embodiment 2：Use Na2PtCl6Do Pt sources and prepare hollow Pt-Ag nano wires (Pt and Ag mol ratios are 0.12).
At normal temperatures, 3.2mg H are taken2PtCl6With 10mg AgNO3It is dissolved in 20mL ethylene glycol, adds 15mg Vitamin Cs
Acid, adds 0.4mL diallyl dimethyl ammoniumchlorides, after ultrasonic dissolution is complete, and arrest reaction 20h, obtains ash at room temperature
The hollow Pt-Ag nano wires of brown.Reaction solution in bottle is moved on in centrifuge tube, 10 minutes (10000 revs/min), precipitum are centrifuged
It is dispersed in water again, then centrifugal sedimentation again, repeats sedimentation and centrifugal process 3 times, removes accessory substance in solution and many
Remaining solvent and protective agent, finally can obtain pure hollow Pt-Ag nano wires.
Embodiment 3：Use K2PtCl6Do Pt sources and prepare hollow Pt-Ag nano wires (Pt and Ag mol ratios are 0.12).
At normal temperatures, 3.4mg H are taken2PtCl6With 10mg AgNO3It is dissolved in 20mL ethylene glycol, adds 15mg Vitamin Cs
Acid, adds 0.4mL diallyl dimethyl ammoniumchlorides, after ultrasonic dissolution is complete, and arrest reaction 20h, obtains ash at room temperature
The hollow Pt-Ag nano wires of brown.Reaction solution in bottle is moved on in centrifuge tube, 10 minutes (10000 revs/min), precipitum are centrifuged
It is dispersed in water again, then centrifugal sedimentation again, repeats sedimentation and centrifugal process 3 times, removes accessory substance in solution and many
Remaining solvent and protective agent, finally can obtain pure hollow Pt-Ag nano wires.
Embodiment 4：Use Na2PdCl4Do Pd sources and prepare hollow Pd-Ag nano wires (Pd and Ag mol ratios are 1).
At normal temperatures, 16.7mg Na are taken2PdCl4With 10mg AgNO3It is dissolved in 20mL ethylene glycol, adds 99mg anti-bad
Hematic acid, adds 0.4mL diallyl dimethyl ammoniumchlorides, after ultrasonic dissolution is complete, and arrest reaction 20h, is obtained at room temperature
The hollow Pt-Ag nano wires of taupe.Reaction solution in bottle is moved on in centrifuge tube, 10 minutes (10000 revs/min), sedimentation are centrifuged
Thing is dispersed in water again, then centrifugal sedimentation again, repeats sedimentation and centrifugal process 3 times, remove accessory substance in solution and
Excess of solvent and protective agent, finally can obtain pure hollow Pd-Ag nano wires.
Embodiment 5：Use K2PdCl4Do Pd sources and prepare hollow Pd-Ag nano wires (Pd and Ag mol ratios are 1).
At normal temperatures, 20.8mg K are taken2PdCl4With 10mg AgNO3It is dissolved in 20mL ethylene glycol, adds 99mg Vitamin Cs
Acid, adds 0.4mL diallyl dimethyl ammoniumchlorides, after ultrasonic dissolution is complete, and arrest reaction 20h, obtains ash at room temperature
The hollow Pt-Ag nano wires of brown.Reaction solution in bottle is moved on in centrifuge tube, 10 minutes (10000 revs/min), precipitum are centrifuged
It is dispersed in water again, then centrifugal sedimentation again, repeats sedimentation and centrifugal process 3 times, removes accessory substance in solution and many
Remaining solvent and protective agent, finally can obtain pure hollow Pd-Ag nano wires.
Embodiment 6：Use H2PtCl6Do Pt sources and prepare hollow Pt-Ag nano wires (Pt and Ag mol ratios are 1).
At normal temperatures, 5.8mg H are taken2PtCl6With 2mg AgNO3It is dissolved in 20mL ethylene glycol, adds 15mg Vitamin Cs
Acid, adds 0.4mL polyallyl alkyl dimethyl ammonium chlorides, after ultrasonic dissolution is complete, at room temperature arrest reaction 20h, obtains ash brown
The hollow Pt-Ag nano wires of color.Reaction solution in bottle is moved on in centrifuge tube, 10 minutes (10000 revs/min) are centrifuged, precipitum is again
Secondary to be dispersed in water, then centrifugal sedimentation again repeats sedimentation and centrifugal process 3 times, removes accessory substance in solution and unnecessary
Solvent and protective agent, finally can obtain pure hollow Pt-Ag nano wires.
Embodiment 7：Use H2PtCl6Do Pt sources and prepare hollow Pt-Ag nano wires (Pt and Ag mol ratios are 5).
At normal temperatures, 29mg H are taken2PtCl6With 2mg AgNO3It is dissolved in 20mL ethylene glycol, adds 15mg ascorbic acid,
0.4mL polyallyl alkyl dimethyl ammonium chlorides are added, after ultrasonic dissolution is complete, arrest reaction 20h, is obtained in taupe at room temperature
Empty Pt-Ag nano wires.Reaction solution in bottle is moved on in centrifuge tube, 10 minutes (10000 revs/min) are centrifuged, precipitum divides again
Dissipate in water, then centrifugal sedimentation again, repeat sedimentation and centrifugal process 3 times, remove accessory substance and excess of solvent in solution
And protective agent, it finally can obtain pure hollow Pt-Ag nano wires.
Surveyed the hollow Pt-Ag or Pd-Ag nano wires obtained by above-described embodiment as electrode for methanol oxidation
Examination, as a result the hollow nano wires of M-Ag of the invention, which are shown, has the activity higher than commercial catalysts.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.
Claims (9)
1. a kind of preparation method of hollow noble metal nano wire, it includes M metal precursors and AgNO3Dissolving in a solvent, is added
Reducing agent, adds protective agent, carries out reacting obtained noble metal nano wire again after being well mixed；Wherein described protective agent is poly- two
Allyl dimethyl ammonium chloride, the temperature of the reaction is 25 DEG C；The reaction time is 15-20hr；M metal precursors and Ag
Mol ratio be (0.1-10):1；The M is Pt or Pd.
2. preparation method according to claim 1, it is characterised in that M metal precursors and Ag mol ratio (1-5):1.
3. preparation method according to claim 1 or 2, it is characterised in that M metal precursors and AgNO3Mol ratio be
(1-5):1, the reducing agent is ascorbic acid, and the mol ratio of ascorbic acid and M metal precursors is 5:1.
4. preparation method according to claim 1 or 2, it is characterised in that the M metal precursors include Pt salt, Pt acid
At least one of with Pd salt；The Pt acid is H2PtCl6；The Pt salt is Na2PtCl6And/or K2PtCl；The Pd salt is
K2PdCl4And/or Na2PdCl4。
5. preparation method according to claim 1 or 2, it is characterised in that the time of the reaction is 20hr.
6. preparation method according to claim 1, it is characterised in that the volume ratio of the protectant aqueous solution and solvent is 1:
50。
7. preparation method according to claim 1, it is characterised in that in protectant aqueous solution, the protection
The mass concentration of agent is 20% to 35%.
8. preparation method according to claim 1, it is characterised in that the solvent is polyalcohol.
9. preparation method according to claim 8, it is characterised in that the polyalcohol includes ethylene glycol, glycerine, penta 2
At least one of alcohol and diethylene glycol.
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