CN105537617B - Method for preparing hollow PtPd nano material with cuprous oxide as template - Google Patents
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 24
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title abstract description 10
- 229940112669 cuprous oxide Drugs 0.000 title abstract 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000000243 solution Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 claims description 54
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 238000010668 complexation reaction Methods 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 2
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 239000000376 reactant Substances 0.000 abstract description 7
- 101150003085 Pdcl gene Proteins 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 238000007323 disproportionation reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0549—Hollow particles, including tubes and shells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for preparing a hollow PtPdnano material with cuprous oxide as a template. The method comprises the following steps that (1) the cuprous oxide is uniformly dispersed into water, an aqueous solution containing PtCl＜6＞＜2-＞ and PdCl＜4＞＜2-＞ is added under the stirring condition at the temperature of 20-25 DEG C, and a stirring reaction is conducted for 30-60 minutes at the temperature; (2) the reaction system in the step (1) is moved into a heating device and heated to the temperature of 60-65 DEG C at the heating speed of 1-3 DEG C/min, and the reaction continues to be conducted for 90-120 minutes at the temperature; and (3) after the reaction is finished, cuprous oxide cores are removed, and the hollow PtPd nano material is obtained. According to the hollow PtPd nano material obtained through the method, the shape of the cuprous oxide template is accurately duplicated, the atomic ratio Pt/Pd of the nano PtPd nano material is made to be close to the atomic ratio Pt/Pd of the reaction solution, the requirement for the stoichiometric ratio of reactants is met, and accurate component controlling is achieved.
Description
Technical field
The present invention relates to hollow nano-material technical field, and in particular to one kind is prepared hollow with Red copper oxide as template
The method of PtPd nano materials.
Background technology
Hollow nano-material has big specific surface area and abundant pore structure, small component units, can accommodate
Substantial amounts of guest molecule or larger-size molecule so as in actual applications with unique performance.And hollow PtPd nanometers
Material combines the advantage of hollow-core construction and noble metal nano particles, with density is low, specific surface area big, high stability and surface
The properties such as permeability, energy is poisoned compared with unit Pt catalyst with more active sites and higher resisting chloride ion penetration
Power, electro catalytic activity is increased substantially so as to have special application front in fields such as biochemistry, catalysis, material science
Scape.It is reported that cube hollow PtPd nano materials have the electro catalytic activity more excellent than other patterns, therefore prepare cube sky
Heart PtPd nano materials are just particularly important.
Cu2O is a kind of P-type semiconductor, has more application in energy storage, catalysis and sensor field.Cu2O/Cu oxidoreductions
Electricity is to being worth (- 0.36V) than precious metals pt Cl6 2-/Pt(0.735V)、PdCl4 2-/Pd (0.987V) is much lower, therefore Cu2O can
With with PtCl6 2-、PdCl4 2- there is spontaneous oxidation reduction reaction so as to reach the mesh in its Surface coating Pt, Pd precious metal element
, finally remove the Cu of inside2O templates can be obtained by hollow PtPd nano materials.
Composition Control is an one of difficult problem when preparing hollow PtPd nano materials for template currently with Red copper oxide.
Chloroplatinic acid and chlorine palladium acid sodium are different from the reactivity of Red copper oxide, and chlorine palladium acid sodium preferentially can react to form one layer with Red copper oxide
The shell of rich Pd, and now the chloroplatinic acid of relative inertness needs diffusion to penetrate shell ability and Cu2O reacts, therefore causes final
The content of Pt will not be met in reaction solution well below the content of Pt in reaction solution, the composition of final product in hollow-core construction
The stoichiometric proportion (atomic ratio Pt/Pd) of noble metal.Reaction at relatively high temperatures can effectively strengthen the diffusivity of chloroplatinic acid,
More chloroplatinic acids are made to penetrate rich Pd shells and Cu2O reacts, so that the composition of final product meets noble metal in reaction solution
Stoichiometric proportion.But chloroplatinic acid and chlorine palladium acid sodium and Cu under heating condition2The redox reaction of O is very violent, causes
Final product surface is extremely coarse, it is impossible to accurately replicate Cu2The pattern of O templates.
Therefore, how to obtain and accurate replicate Red copper oxide template pattern and meet reactant stoichiometric proportion (i.e. end-product
Atomic ratio Pt/Pd and reaction solution in atomic ratio Pt/Pd it is close) hollow PtPd nano materials just become a difficulty
Topic.
The content of the invention
In view of this, it is an object of the invention to provide one kind prepares hollow PtPd nano materials by template of Red copper oxide
Method, be obtained in that and accurate replicate Red copper oxide template pattern and meet the hollow PtPd nanometers material of reactant stoichiometric proportion
Material.
To reach above-mentioned purpose, the present invention provides following technical scheme：
A kind of method for preparing hollow PtPd nano materials as template with Red copper oxide, comprises the following steps：
(1) Red copper oxide is dispersed in water, adds under 20-25 DEG C of stirring condition and contain PtCl6 2- and
PdCl4 2- aqueous solution, stirring reaction 30-60min at this temperature；
(2) reaction system of step (1) is moved into into heater and is heated to 60-65 DEG C with the heating rate of 1-3 DEG C/min,
Continue at this temperature to react 90-120min；
(3) Red copper oxide core is removed after the completion of reacting, hollow PtPd nano materials are obtained.
Further, the Red copper oxide is the Red copper oxide of cubic structure.
Further, the Red copper oxide of the cubic structure is prepared by following methods：It is past under 50-60 DEG C of stirring condition
CuCl2Add excessive NaOH solution to react 0.5-1h in solution, ascorbic acid solution is then slowly added dropwise again, after reaction 3-4h
Centrifugation, then be finally vacuum dried with water and ethanol purge respectively, obtain the Red copper oxide of cubic structure.
Further, in the step (1), containing PtCl6 2- and PdCl4 2- aqueous solution be H2PtCl6And Na2PdCl4It is mixed
Heshui solution.
Further, in the step (1), the PtCl of addition6 2- and PdCl4 2- sum is with the mol ratio of Red copper oxide
1.4-2.3∶1。
Further, in the step (3), product is centrifuged into 2-5min under the conditions of 4000-10000 turns after the completion of reaction,
The ammonia complexation for adding 18%-25% removes Red copper oxide core, obtains hollow PtPd nano materials.
Further, in the step (3), after removing Red copper oxide core, the nitric acid of 0.1-0.5mol/L is added at 10-25 DEG C
Lower reaction removes the copper that dismutation reaction is produced.
The beneficial effects of the present invention is：
The present invention is segmented the technology controlling and process course of reaction kinetics of reaction, the hollow PtPd nanometers material for obtaining using multi-temperature
Material had both accurately replicated the pattern of Red copper oxide template, the atomic ratio Pt/Pd of hollow PtPd nano materials is caused again and reacts molten
Atomic ratio Pt/Pd in liquid is close, meets reactant stoichiometric proportion, realizes accurate Composition Control.
Description of the drawings
In order that the purpose of the present invention, technical scheme and beneficial effect are clearer, the present invention provides drawings described below and carries out
Explanation：
Fig. 1 is the stereoscan photograph of cube hollow PtPd nano materials prepared by embodiment 1；
Fig. 2 is the stereoscan photograph of cube hollow PtPd nano materials prepared by comparative example 1；
Fig. 3 is the stereoscan photograph of cube hollow PtPd nano materials prepared by comparative example 2.
Specific embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.
According to Red copper oxide pattern and the multiformity of size, the hollow PtPd nanometers material of different structure can be designed and synthesized
Material, following examples and comparative example are by taking the Red copper oxide of cubic structure as an example.
The Red copper oxide of the cubic structure that following examples and comparative example are used is prepared by following methods：
Under 55 DEG C of stirring conditions, to the CuCl that 100ml concentration is 0.01mol/L2Addition 10mL concentration is in solution
The NaOH solution of 2mol/L, after reaction 0.5h, then is slowly added dropwise the ascorbic acid solution that 10ml concentration is 0.6mol/L, instead
After answering 3h, centrifugation, respectively with water and ethanol purge, last 40 DEG C of vacuum drying 12h obtains the Red copper oxide of cubic structure.
Embodiment 1
The method for preparing hollow PtPd nano materials as template with Red copper oxide of embodiment 1, comprises the following steps：
(1) the Red copper oxide ultrasound of 10mg cubic structures is dispersed in 10ml water, is added under 20 DEG C of stirring conditions
Enter the H of 20mM2PtCl6The Na of aqueous solution and 33mM2PdCl4Aqueous solution, make atomic ratio Pt/Pd in reaction solution be 4: 1,
PtCl6 2- and PdCl4 2- sum is 1.4: 1 with the mol ratio of Red copper oxide, at this temperature stirring reaction 60min；
(2) reaction system of step (1) is moved into into heater and is heated to 60 DEG C with the heating rate of 1 DEG C/min, here
At a temperature of continue react 120min；
(3) product is centrifuged into 5min under the conditions of 5000 turns after the completion of reacting, the ammonia complexation for adding 20% removes oxidation
Cuprous core, is subsequently adding the nitric acid of 0.1mol/L and reacts at 25 DEG C and remove the copper that dismutation reaction is produced, and obtains cube hollow
PtPd nano materials.
Embodiment 2
The method for preparing hollow PtPd nano materials as template with Red copper oxide of embodiment 2, comprises the following steps：
(1) the Red copper oxide ultrasound of 10mg cubic structures is dispersed in 10ml water, is added under 22 DEG C of stirring conditions
Enter the H of 20mM2PtCl6The Na of aqueous solution and 33mM2PdCl4Aqueous solution, make atomic ratio Pt/Pd in reaction solution be 4: 1,
PtCl6 2- and PdCl4 2- sum is 2.0: 1 with the mol ratio of Red copper oxide, at this temperature stirring reaction 50min；
(2) reaction system of step (1) is moved into into heater and is heated to 62 DEG C with the heating rate of 2 DEG C/min, here
At a temperature of continue react 100min；
(3) product is centrifuged into 4min under the conditions of 8000 turns after the completion of reacting, the ammonia complexation for adding 25% removes oxidation
Cuprous core, is subsequently adding the nitric acid of 0.2mol/L and reacts at 20 DEG C and remove the copper that dismutation reaction is produced, and obtains cube hollow
PtPd nano materials.
Embodiment 3
The method for preparing hollow PtPd nano materials as template with Red copper oxide of embodiment 3, comprises the following steps：
(1) the Red copper oxide ultrasound of 10mg cubic structures is dispersed in 10ml water, is added under 25 DEG C of stirring conditions
Enter the H of 20mM2PtCl6The Na of aqueous solution and 33mM2PdCl4Aqueous solution, make atomic ratio Pt/Pd in reaction solution be 4: 1,
PtCl6 2- and PdCl4 2- sum is 2.3: 1 with the mol ratio of Red copper oxide, at this temperature stirring reaction 30min；
(2) reaction system of step (1) is moved into into heater and is heated to 65 DEG C with the heating rate of 3 DEG C/min, here
At a temperature of continue react 90min；
(3) product is centrifuged into 3min under the conditions of 10000 turns after the completion of reacting, the ammonia complexation for adding 25% removes oxidation
Cuprous core, is subsequently adding the nitric acid of 0.5mol/L and reacts at 10 DEG C and remove the copper that dismutation reaction is produced, and obtains cube hollow
PtPd nano materials.
Comparative example 1
The method for preparing hollow PtPd nano materials as template with Red copper oxide of comparative example 1, comprises the following steps：
(1) the Red copper oxide ultrasound of 10mg cubic structures is dispersed in 10ml water, is added under 20 DEG C of stirring conditions
Enter the H of 20mM2PtCl6The Na of aqueous solution and 33mM2PdCl4Aqueous solution, make atomic ratio Pt/Pd in reaction solution be 4: 1,
PtCl6 2- and PdCl4 2- sum is 1.4: 1 with the mol ratio of Red copper oxide, stirring reaction 180min under 20 DEG C of constant temperatures；
(2) product is centrifuged into 5min under the conditions of 5000 turns after the completion of reacting, the ammonia complexation for adding 20% removes oxidation
Cuprous core, is subsequently adding the nitric acid of 0.1mol/L and reacts at 25 DEG C and remove the copper that dismutation reaction is produced, and obtains cube hollow
PtPd nano materials.
Comparative example 2
The method for preparing hollow PtPd nano materials as template with Red copper oxide of comparative example 2, comprises the following steps：
(1) the Red copper oxide ultrasound of 10mg cubic structures is dispersed in 10ml water, is added under 60 DEG C of stirring conditions
Enter the H of 20mM2PtCl6The Na of aqueous solution and 33mM2PdCl4Aqueous solution, make atomic ratio Pt/Pd in reaction solution be 4: 1,
PtCl6 2- and PdCl4 2- sum is 1.4: 1 with the mol ratio of Red copper oxide, stirring reaction 180min under 60 DEG C of constant temperatures；
(2) product is centrifuged into 5min under the conditions of 5000 turns after the completion of reacting, the ammonia complexation for adding 20% removes oxidation
Cuprous core, is subsequently adding the nitric acid of 0.1mol/L and reacts at 25 DEG C and remove the copper that dismutation reaction is produced, and obtains cube hollow
PtPd nano materials.
The stereoscan photograph of cube hollow PtPd nano materials prepared by embodiment 1, comparative example 1 and comparative example 2 is as schemed
Shown in 1-3, the inductively coupled plasma of cube hollow PtPd nano materials prepared by embodiment 1, comparative example 1 and comparative example 2
Emission spectrum (ICP) and roughness test result are as shown in table 1.
The ICP compositions of table 1 and roughness test result
Comparative example 1 is can be seen that from the experimental data of Fig. 1-3 and table 1 to react under 20 DEG C of constant temperatures, although can be accurate
Replicate Cu2The pattern of O templates, but the atomic ratio Pt/Pd of product do not meet well below the atomic ratio Pt/Pd in reaction solution
Reactant stoichiometric proportion；Comparative example 2 is reacted under 60 DEG C of constant temperatures, although meet reactant stoichiometric proportion, but product
Surface is extremely coarse, it is impossible to accurately replicate Cu2The pattern of O templates；And embodiment 1 is by using multi-temperature segmentation reaction, obtaining
Hollow PtPd nano materials both accurately replicated Cu2The pattern of O templates, causes the atomic ratio Pt/Pd of product and reacts molten again
Atomic ratio Pt/Pd in liquid is close, meets reactant stoichiometric proportion, realizes accurate Composition Control.
Finally illustrate, preferred embodiment above is only unrestricted to illustrate technical scheme, although logical
Cross above preferred embodiment to be described in detail the present invention, it is to be understood by those skilled in the art that can be
In form and in details various changes are made to it, without departing from claims of the present invention limited range.
Claims (7)
1. a kind of method that hollow PtPd nano materials are prepared as template with Red copper oxide, it is characterised in that：Including following step
Suddenly：
（1）Red copper oxide is dispersed in water, is added under 20-25 DEG C of stirring condition and is contained PtCl6 2‒And PdCl4 2‒Water
Solution, at this temperature stirring reaction 30-60min；
（2）By step（1）Reaction system move into heater be heated to 60-65 DEG C with the heating rate of 1-3 DEG C/min, here
At a temperature of continue react 90-120min；
（3）Red copper oxide core is removed after the completion of reaction, hollow PtPd nano materials are obtained.
2. the method for preparing hollow PtPd nano materials as template with Red copper oxide according to claim 1, its feature exists
In：The Red copper oxide is the Red copper oxide of cubic structure.
3. the method for preparing hollow PtPd nano materials as template with Red copper oxide according to claim 2, its feature exists
In：The Red copper oxide of the cubic structure is prepared by following methods：Under 50-60 DEG C of stirring condition, toward CuCl2Add in solution
Excessive NaOH solution reaction 0.5-1h, is then slowly added dropwise again ascorbic acid solution, is centrifuged after reaction 3-4h, then uses water respectively
And ethanol purge, finally it is vacuum dried, obtain the Red copper oxide of cubic structure.
4. the method for preparing hollow PtPd nano materials as template with Red copper oxide according to claim 1, its feature exists
In：The step（1）In, containing PtCl6 2‒And PdCl4 2‒Aqueous solution be H2PtCl6And Na2PdCl4Mixed aqueous solution.
5. the method for preparing hollow PtPd nano materials as template with Red copper oxide according to claim 1, its feature exists
In：The step（1）In, the PtCl of addition6 2‒And PdCl4 2‒Sum is 1.4-2.3 with the mol ratio of Red copper oxide:1.
6. the method for preparing hollow PtPd nano materials as template with Red copper oxide according to claim 1, its feature exists
In：The step（3）In, product is centrifuged into 2-5min under the conditions of 4000-10000 turns after the completion of reaction, add 18%-25%'s
Ammonia complexation removes Red copper oxide core, obtains hollow PtPd nano materials.
7. the method for preparing hollow PtPd nano materials as template with Red copper oxide according to claim 1, its feature exists
In：The step（3）In, after removing Red copper oxide core, the nitric acid for adding 0.1-0.5mol/L reacts removal discrimination at 10-25 DEG C
Change the copper that reaction is produced.
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| JP2008019461A (en) * | 2006-07-11 | 2008-01-31 | Fujifilm Corp | Method for manufacturing metal nanoparticle, metal nanoparticle, and metal nanoparticle dispersion |
| CN101690977B (en) * | 2009-09-14 | 2011-06-01 | 西安交通大学 | Preparation method of hollow noble metal nanoparticles |
| JP5450725B2 (en) * | 2011-08-30 | 2014-03-26 | 富士フイルム株式会社 | Collagen peptide-coated copper nanoparticles, collagen peptide-coated copper nanoparticle dispersion, method for producing collagen peptide-coated copper nanoparticles, conductive ink, method for producing conductive film, and conductor wiring |
| CN102581296A (en) * | 2012-01-12 | 2012-07-18 | 北京理工大学 | Method for improving efficiency of hollow sphere preparation by template dissolving method |
| CN103042231B (en) * | 2013-01-11 | 2014-09-03 | 哈尔滨工业大学 | Preparation method of precious metal nano-particles |
| CN103170648B (en) * | 2013-04-09 | 2014-11-12 | 厦门大学 | Preparation method of hollow metal microspheres |
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