CN105932308B - The preparation method of nanometer electrical catalyst - Google Patents
The preparation method of nanometer electrical catalyst Download PDFInfo
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- CN105932308B CN105932308B CN201610445365.4A CN201610445365A CN105932308B CN 105932308 B CN105932308 B CN 105932308B CN 201610445365 A CN201610445365 A CN 201610445365A CN 105932308 B CN105932308 B CN 105932308B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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Abstract
A kind of preparation method of nanometer electrical catalyst, including：Metal carbonyl clusterses solution is provided, the metal carbonyl clusterses include platinum and the first metal；The carrying capacity of platinum and the first metal in the metal carbonyl clusterses is adjusted to 20%~100%；Oxidizing gas is passed through into the metal carbonyl clusterses solution, and adds reducing agent, is reacted；Reacted product is dried；Dried product exhibited is heat-treated.The above method can prepare that particle diameter is small, and the high-performance nano elctro-catalyst that component is controllable.
Description
Technical field
The present invention relates to elctro-catalyst field, more particularly to a kind of preparation method of nanometer electrical catalyst.
Background technology
Proton Exchange Membrane Fuel Cells is a kind of energy conversion device that chemical energy is converted into electric energy, and it has energy
It is high to measure transformation efficiency, easily starts, it is pollution-free the advantages that, it is considered to be one of following optimal energy.However, fuel cell is extensive
The elctro-catalyst used is Pt sills.Due to platinum scarcity of resources, expensive, fuel cell cost is caused to remain high, into
One of obstacle for commercializing fuel cells.It is material nano to reduce one of fuel cell cost, effective strategy, most
The utilization rate of the lifting material of limits, while binary metal is introduced into Pt lattices, form alloy with Pt.Due to introducing
Structure effect, electronic effect and ligand effect are formed between second yuan of metallic element atom and Pt atoms, Pt catalysis can be strengthened
The electrocatalysis characteristics such as antitoxinization performance, electro catalytic activity and the durability of agent.
The electrocatalysis characteristic of catalyst and particle size itself, composition, structure and pattern are closely related.For example, atom
Than for 1:1, there is the Pt-Ru alloys of small particle, due to difunctional effect be considered as to anodic oxidation of methanol most
Good catalyst；Pt-Co, Pt-Ni catalyst are current report highest to the catalytic performance of oxygen reduction activity.In addition, proton
Exchange film fuel battery is in actual application, to improve inside battery reactant, product and the transmission of intermediate product, drop
The low internal resistance of cell, generally require using the high catalyst of metal ladings, wherein metal quality fraction wt >=50%, but preparing
During, high metal ladings would generally cause metal nanoparticle reunion or condensation growth, so as to cause the activity of catalyst
Specific surface area declines, and causes the utilization rate of Pt materials to reduce.
Therefore, how to obtain metal ladings are high, particle diameter is small, composition is controllable, pattern is homogeneous, can prepare with scale nanometer it is electric
Catalyst is one of challenge of research.Current document report is more to be less than using surfactant, stabilizer as auxiliary preparation carrying capacity
40wt% nanometer electrical catalyst, very big inconvenience is caused in actual production and application, such as：Surfactant is more difficult generally
Remove, easily remain in nanoparticle surface, reduce nanometer electrical catalyst performance.
So the preparation method of nanometer electrical catalyst needs further to be improved, to be formed, particle diameter is small and electrocatalysis characteristic
High nanometer electrical catalyst.
The content of the invention
The technical problem to be solved by the invention is to provide a kind of preparation method of Nanoalloy elctro-catalyst.
In order to solve the above problems, the invention provides a kind of preparation method of Nanoalloy elctro-catalyst, including：There is provided
Metal carbonyl clusterses solution, the metal carbonyl clusterses include platinum and the first metal；By in the metal carbonyl clusterses
The carrying capacity of platinum and the first metal is adjusted to 20%~100%；Oxidizing gas is passed through into the metal carbonyl clusterses solution,
And reducing agent is added, reacted；Reacted product is dried；Dried product exhibited is heat-treated.
It is optionally, described that the temperature of metal carbonyl clusterses solution is 20 DEG C~100 DEG C when being reacted, reducing agent with
The mol ratio of first metal is 5~25:1.
Optionally, first metal is one kind in Fe, Co, Ni, Cr, Cu, Ru, Pd and Ag.
Optionally, preparing the method for metal carbonyl clusterses solution includes：By compound containing platinum and containing the first metal compound
Thing dissolves to form solution；Sodium acetate and sodium hydroxide are added into the solution, to adjust the pH value of the solution as 7~13；
Carbon monoxide is passed through into the solution, it is 20 DEG C~80 DEG C to keep solution temperature, is maintained 2 hours~24 hours.
Optionally, carrier is added into the metal carbonyl clusterses solution or sacrifices template to adjust the metal-carbonyl
The carrying capacity of platinum and the first metal in cluster compound.
Optionally, the material of the carrier includes at least one of carbon black, graphene, CNT and mesoporous carbon；Institute
Stating sacrifice mould material includes at least one of nano magnesia, nano aluminium oxide and nano zine oxide.
Optionally, in addition to：Product after heat treated adds acid solution, to remove the sacrifice template.
Optionally, the acid solution is one kind in sulfuric acid, hydrochloric acid, nitric acid and perchloric acid.
Optionally, the reducing agent includes：One kind in sodium borohydride, hydrazine hydrate and ascorbic acid.
Optionally, the temperature of the heat treatment is 100 DEG C~800 DEG C, and the time is 2 hours~20 hours.
The present invention is used as catalyst precursors by preparing metal carbonyl clusterses, and by carrier or sacrifices template adjustment
After metal ladings, coreduction and heat treatment are carried out to metal carbonyl clusterses, obtain the electro-catalysis that particle diameter is small, composition is controllable
Agent, surfactant is not needed to participate in course of reaction, so as to improve the performance of the nanometer electrical catalyst prepared.
Brief description of the drawings
Fig. 1 is the flow chart of the preparation method of the nanometer electrical catalyst of the embodiment of the present invention；
Fig. 2 be the present invention embodiment in the load for preparing be C, the PtCo nanometer electricity that carrying capacity is 40% urges
The X ray diffracting spectrum of agent；
Fig. 3 be the present invention embodiment in the load for preparing be C, the PtCo nanometer electricity that carrying capacity is 40% urges
The transmission electron microscope photo of agent；
Fig. 4 be the present invention embodiment in the load for preparing be C, the PtCo nanometer electricity that carrying capacity is 70% urges
The transmission electron microscope photo of agent；
Fig. 5 be the present invention embodiment in the load for preparing be C, the PtCo nanometer electricity that carrying capacity is 70% urges
The X ray diffracting spectrum of agent；
Fig. 6 be the present invention embodiment in the load for preparing be C, the PtRu nanometer electricity that carrying capacity is 20% urges
The transmission electron microscope photo of agent；
Fig. 7 is the X ray of the non-loaded PtRu nanometer electrical catalysts prepared in the embodiment of the present invention
Diffracting spectrum；
Fig. 8 be the present invention embodiment in the load for preparing be C, the PtNi nanometer electricity that carrying capacity is 60% urges
The X ray diffracting spectrum of agent.
Embodiment
The embodiment of the preparation method of nanometer electrical catalyst provided by the invention is done in detail below in conjunction with the accompanying drawings
Explanation.
Fig. 1 is refer to, for the schematic flow sheet of the preparation method of the nanometer electrical catalyst of the present invention.
Step S101：Metal carbonyl clusterses solution is prepared, the metal carbonyl clusterses include platinum and the first metal.
It can use that to form the metal carbonyl clusterses the methods of redox, redox condensation and thermal condensation molten
Liquid.
As the specific embodiment of the present invention, preparing the method for metal carbonyl clusterses solution includes：By platiniferous
Compound and dissolve to form solution containing the first metallic compound；Sodium acetate and sodium hydroxide are added into the solution, with regulation
The pH value of the mixed solution is 7~13；Carbon monoxide is passed through into the solution, it is 20 DEG C~80 DEG C to keep solution temperature,
Maintain 2 hours~24 hours, obtain the metal carbonyl clusterses solution.
According to target composition weigh the compound containing platinum and containing the first metallic compound after, be dissolved in methanol, nitrile or
In toluene solution, stir to being completely dissolved, form the mixed solution.
Specifically, the compound containing platinum includes：Platinic sodium chloride, chloroplatinic acid, potassium chloroplatinate, ammonium chloroplatinate, the first metal
It can be one kind in Fe, Co, Ni, Cr, Cu, Ru, Pd and Ag.First metallic atom can form alloy with pt atom,
With structure effect, electronic effect and ligand effect, platinum catalyst performance can be strengthened.
First metallic compound that contains includes：Cobalt chloride, ruthenic chloride, iron chloride, nickel acetate, chromium chloride, copper chloride, chlorine
Change palladium or silver chlorate etc..
Presoma of the metal carbonyl clusterses as nanometer electrical catalyst to be prepared.
Step S102：The carrying capacity of platinum and the first metal in the metal carbonyl clusterses is adjusted to 20%~100%.
The metal carbonyl can be adjusted by adding carrier into the metal carbonyl clusterses solution or sacrificing template
The carrying capacity of platinum and the first metal in base cluster compound so that in metal carbonyl clusterses, the mass fraction of the platinum and the first metal
For 20%~100%, i.e., carrying capacity is 20%~100%.Add carrier or stirred after sacrificing template, it is uniformly dispersed.
The material of the carrier can include at least one of carbon black, graphene, CNT and mesoporous carbon.The load
Body can also play space obstacle effect in subsequent heat treatment, avoid that nanometer agglomeration occurs.
The sacrifice mould material includes at least one of nano magnesia, nano aluminium oxide and nano zine oxide.
Step S103：Oxidizing gas is passed through into the metal carbonyl clusterses solution, and adds reducing agent, is carried out anti-
Should.
Specifically, in course of reaction, the metal carbonyl clusterses solution temperature can be adjusted in 20 DEG C~100 DEG C
Any temperature, the grain of the nanometer electrical catalyst ultimately formed can be adjusted by adjusting metal carbonyl clusterses solution temperature
Footpath size.
The oxidizing gas can be air, oxygen or O3Deng by the oxidizing gas by carbonyl platinum oxidation, shape
Into Pt atoms.
The reducing agent can be the material that sodium borohydride, hydrazine hydrate or ascorbic acid etc. have reproducibility, for will be molten
The first metal ion in liquid reduces to form atom or metallic state.The reducing agent forms reductant solution after can dissolving and added again
Enter in the metal carbonyl clusterses solution.
The mol ratio of the reducing agent and the first metal can be 5~25:1, can be by adjusting the reducing agent and
The mol ratio of one metal adjusts the particle size of the nanometer electrical catalyst ultimately formed.
As the specific embodiment of the present invention, the time of the reaction is 8 hours~24 hours.
Step S104：Reacted product is dried.
Such as：Dried 4 hours in the environment of 60 DEG C, obtain dried product exhibited.
Step S105：Dried product exhibited is heat-treated.
As the specific embodiment of the present invention, the heat treatment is carried out under reducing atmosphere or inert atmosphere, is kept away
Exempt from product to react with environmental gas, the reducing atmosphere can be H2, the inert atmosphere can be Ar, He, Ne or N2,
Reducing atmosphere and inert atmosphere can also be included simultaneously.The temperature of heat treatment is 100 DEG C~800 DEG C, and the time is 2 hours~20 small
When, after heat treatment, nitrogen can be passed through to be cooled down, such as be passed through nitrogen 30~50 minutes.
It is described to be heat-treated for forming the alloy nano elctro-catalyst of platinum and the first metal, and it is possible to remove described receive
The impurity such as the oxide on rice electrocatalyst particles surface, hydroxy compounds.
In the embodiment of the present invention, if in step S102, sacrificing template by adding to adjust metal-carbonyl
The carrying capacity of platinum and the first metal in cluster compound, then after being heat-treated, it is also necessary to which the product after heat treated adds acid
Solution, to remove the sacrifice template.
The acid solution can be one kind in sulfuric acid, hydrochloric acid, nitric acid and perchloric acid.
The processing such as subsequently the catalyst of acquisition can also be cleaned, filtered and be dried, it is miscellaneous in catalyst to remove
Matter ion, such as halogen ion.
The particle diameter high-performance nano alloy elctro-catalyst controllable less than 5nm, composition can be prepared according to the method described above.
It is multiple embodiments that nanometer electrical catalyst is prepared using the above method below.
1st, the loaded nano elctro-catalyst for the PtCo/C that preparation carrying capacity is 40%, Pt and Co mol ratio are 1:1.
Specific method includes：(1) preparation of metal carbonyl clusterses solution：It is Pt in molar ratio：Co=1:1 ratio weighs
Containing platinic sodium chloride and cobalt chloride dissolving in methyl alcohol, stirring forms mixed solution to being completely dissolved；To it is described dissolved with metal from
Sodium acetate and sodium hydroxide are added in the mixed solution of son, controls pH value of solution=7；Carbon monoxide gas is passed through into reaction system again
Body, kept for 20 DEG C react 2 hours, obtain metal carbonyl clusterses solution.
(2) injection of carrier：Quantitative carbon black is added into solution, adjustment Pt and Co carrying capacity is 40%, and continuing stirring makes
It is uniformly dispersed.
(3) coreduction of metal cluster compound：It is 20 DEG C to keep reaction temperature, is passed through air, the sodium borohydride that will have been configured
Solution is added in reaction system, and sodium borohydride is 5 with Co ions mol ratio:1, continue after reacting 8h, filtration washing, Ran Hou
Dried 4 hours at 60 DEG C.
(4) catalyst is heat-treated：By dried product exhibited in H2Under Ar mixed atmosphere, hot place is carried out in 100 DEG C of conditions
Reason 2 hours, then passes to N230 minutes, product is taken out after cooling down, obtain the PtCo loaded nano electricity that carrying capacity is 40% and urge
Agent, carrier C.Its X ray diffracting spectrum and transmission electron microscope collection of illustrative plates refer to Fig. 2, Fig. 3.In Fig. 2, XRD spectrum shows 6
Peak, wherein being carbon peak at 23 ° or so of peak, remaining 5 peak is Pt peak, be followed successively by from small to large (111), (200), (220),
(311) and (222) crystal face, the oxide peak of oxidation peak and Co and Co without Pt, and compared to Pt simple substance diffraction maximum to height
Position is offset, and is shown that Co enters in Pt lattices, is formed Pt-Co alloys.
2nd, carrying capacity is prepared as 70% PtCo/C loaded nano elctro-catalysts, and Pt and Co mol ratio are 2:1.
(1) preparation of metal carbonyl clusterses solution：It is Pt in molar ratio：Co=2:1 ratio weigh compound containing platinum and
Cobalt chloride dissolves in methyl alcohol, and stirring is to being completely dissolved；Sodium acetate and hydroxide are added into the solution dissolved with metal ion
Sodium, control pH value of solution=13；CO gas is passed through into reaction system again, continues to react 18 hours at 60 DEG C, obtains gold
Belong to Carbonyl Clusters solution.
(2) injection of carrier：Quantitative carbon black is added into solution, the carrying capacity for making Pt and Co is 70%, and continuing stirring makes it
It is uniformly dispersed.
(3) coreduction of metal cluster compound：Air is passed through after reaction system is cooled into 30 DEG C, the hydroboration that will have been configured
Sodium solution is added in reaction system, and sodium borohydride is 25 with Co ions mol ratio:1, continue filtration washing after reaction 24h, so
Dry 4 hours at 60 DEG C afterwards.
(4) catalyst is heat-treated：By dried product exhibited in H2Under Ar mixed atmosphere, hot place is carried out in 200 DEG C of conditions
Reason 20 hours, then passes to N230 minutes, product is taken out after cooling down, obtain the PtCo nanometer electrical catalysts that carrying capacity is 70%,
Loading as C, its transmission electron microscope (TEM) photo refer to Fig. 4, and X-ray diffraction (XRD) collection of illustrative plates refer to Fig. 5, in Fig. 5,
XRD spectrum shows 6 peaks, wherein being carbon peak at 23 ° or so of peak, remaining 5 peak is Pt peak, is followed successively by from small to large
(111), (200), (220), (311) and (222) crystal face, the oxide peak of oxidation peak and Co and Co without Pt, and compare
The diffraction maximum of Pt simple substance is offset to high position, is shown that Co enters in Pt lattices, is formed Pt-Co alloys.
3rd, non-loading type Pt-Co nanometer electrical catalysts are prepared, Pt and Co mol ratio are 1:1.
(1) preparation of metal carbonyl clusterses solution：It is Pt in molar ratio：Co=1:1 ratio weigh compound containing platinum and
Cobalt chloride dissolves in methyl alcohol, and stirring is to being completely dissolved；Sodium acetate and hydroxide are added into the solution dissolved with metal ion
Sodium, control pH value of solution=8；CO gas is passed through into reaction system again to remove in system after air, reacts 20 at 80 DEG C
Hour, obtain metal carbonyl clusterses solution.
(2) template injection is sacrificed：In N2Or under CO gas shields, quantitative oxidation is added into metal carbonyl clusterses solution
Magnesium, continuing stirring makes magnesium oxide dispersion uniform.
(3) coreduction of metal cluster compound：Air is passed through after reaction system is cooled into 20 DEG C, the hydroboration that will have been configured
Sodium solution is added in reaction system, and sodium borohydride is 10 with metal ion mol ratio:1, cross diafiltration after continuing reaction 18 hours
Wash rear 60 DEG C of dryings 4 hours.
(4) catalyst is heat-treated：By dried product exhibited in H2Under Ar mixed atmosphere, heat is carried out under the conditions of 500 DEG C
Processing 2 hours, then passes to N230 minutes, product is set to be taken out after cooling down.
(5) dissolving of template is sacrificed：Continue one section of stirring after a certain amount of sulfuric acid solution is added into the sample after cooling
Time, then dried after filtration washing 5 times, that is, obtain non-loading type Pt-Co nanometer electrical catalysts.
4th, carrying capacity is prepared as 20% PtRu/C loaded nano elctro-catalysts, and Pt and Ru mol ratio are 1:1.
(1) preparation of metal carbonyl clusterses：It is Pt in molar ratio：Ru=1:1 ratio is weighed containing platinic sodium chloride and chlorination
Ruthenium dissolves in methyl alcohol, and stirring is to being completely dissolved；Sodium acetate and sodium hydroxide, control are added into the solution dissolved with metal ion
PH value of solution=7 processed；CO gas is passed through into reaction system again, keeps 20 DEG C of reaction 2h to obtain more metal carbonyl clusterses
Solution.
(2) injection of carrier：Quantitative carbon black is added into solution, it is 20% to make metal ladings, and continuing stirring makes it scattered
Uniformly.
(3) coreduction of metal cluster compound：It is 20 DEG C to keep reaction temperature, is passed through air, the sodium borohydride that will have been configured
Solution is added in reaction system, and sodium borohydride is 5 with Co ions mol ratio:1, continue to react after 8h after filtration washing 60 DEG C it is dry
Dry 4h.
(4) catalyst is heat-treated：By dried product exhibited in H2Under Ar mixed atmospheres, it is heat-treated in 100 DEG C of conditions
After 2h, N is passed through230min, product is taken out after cooling down, obtain the Pt Ru Nanoalloy elctro-catalysts that carrying capacity is 20%, carrier
For C.Its transmission electron microscope picture is shown in Fig. 6.
5th, carrying capacity is prepared as 60% PtRu/C nanometer electrical catalysts, and Pt and Ru mol ratio are 2:1.
(1) preparation of metal carbonyl clusterses solution：It is Pt in molar ratio：Ru=2:1 ratio weigh compound containing platinum and
Ruthenic chloride dissolves in methyl alcohol, and stirring is to being completely dissolved；Sodium acetate and hydroxide are added into the solution dissolved with metal ion
Sodium, control pH value of solution=13；CO gas is passed through into reaction system again, continues to obtain more metals in 60 DEG C of reaction 18h
Carbonyl Clusters solution.
(2) injection of carrier：Quantitative carbon black is added into solution, the carrying capacity for making Pt and Ru is 60%, and continuing stirring makes it
It is uniformly dispersed.
(3) coreduction of metal cluster compound：Air is passed through after reaction system is cooled into 30 DEG C, the hydroboration that will have been configured
Sodium solution is added in reaction system, and sodium borohydride is 25 with metal ion mol ratio:1, continue to react after 24h after filtration washing
60 DEG C of dry 4h.
(4) catalyst is heat-treated：By dried product exhibited in H2Under Ar mixed atmospheres, it is heat-treated in 800 DEG C of conditions
After 20h, N is passed through230min, product is taken out after cooling down, obtain the PtRu Nanoalloy elctro-catalysts that carrying capacity is 60%, carrier
For C.
6th, non-loading type PtRu nanometer electrical catalysts are prepared, Pt and Ru mol ratio are 1:1.
(1) preparation of metal carbonyl clusterses solution：It is Pt in molar ratio：Ru=1:1 ratio weigh compound containing platinum and
Ruthenic chloride dissolves in methyl alcohol, and stirring is to being completely dissolved；Sodium acetate and hydroxide are added into the solution dissolved with metal ion
Sodium, control pH value of solution=8；CO gas is passed through into reaction system again to remove in system after air, reacts 20h at 80 DEG C
Obtain metal carbonyl clusterses solution.
(2) template injection is sacrificed：In N2Or under CO gas shields, quantitative oxidation is added into metal carbonyl clusterses solution
Magnesium, continuing stirring makes magnesium oxide dispersion uniform.
(3) coreduction of metal cluster compound：Air is passed through after reaction system is cooled into 20 DEG C, the hydroboration that will have been configured
Sodium solution is added in reaction system, and sodium borohydride is 10 with Ru ions mol ratio:1, continue filtration washing after reaction 18h,
4h is dried under 60 DEG C of environment.
(4) catalyst is heat-treated：By dried product exhibited in H2Under Ar mixed atmosphere, hot place is carried out in 500 DEG C of conditions
2h is managed, then passes to N230min, product is set to be taken out after cooling down.
(5) dissolving of magnesia：Added into the sample after cooling after a certain amount of sulfuric acid solution when continuing one section of stirring
Between, then dried after filtration washing 5 times, obtain non-loading type PtRu nanometer electrical catalysts.Its X ray collection of illustrative plates is shown in Fig. 7, in Fig. 7,
XRD spectrum shows 5 peaks, and 5 peaks are Pt peak, be followed successively by from small to large (111), (200), (220), (311) and
(222) crystal face, the oxide peak of oxidation peak and Ru and Ru without Pt, and it is inclined to high position compared to the diffraction maximum of Pt simple substance
Move, show that Ru enters in Pt lattices, form Pt-Ru alloys.
7th, carrying capacity is prepared as 60% PtFe/C loaded nano elctro-catalysts, and Pt and Fe mol ratio are 2:1.
(1) preparation of metal carbonyl clusterses solution：It is Pt in molar ratio：Fe=2:1 ratio weigh compound containing platinum and
Iron chloride dissolves in methyl alcohol, and stirring is to being completely dissolved；Sodium acetate and hydroxide are added into the solution dissolved with metal ion
Sodium, control pH value of solution=13；CO gas is passed through into reaction system again, continues to obtain metal carbonyl in 60 DEG C of reaction 18h
Base cluster polymer solution.
(2) injection of carrier：Quantitative carbon black is added into solution, it is 60% to make metal ladings, and continuing stirring makes it scattered
Uniformly.
(3) coreduction of metal cluster compound：Air is passed through after reaction system is cooled into 30 DEG C, the hydroboration that will have been configured
Sodium solution is added in reaction system, and sodium borohydride is 25 with Fe ions mol ratio:1, continue to react after 24h 60 after filtration washing
DEG C dry 4h.
(4) catalyst is heat-treated：By dried product exhibited in H2It is heat-treated with Ar mixed atmospheres in 800 DEG C of conditions
20h, then pass to N230min, product is taken out after cooling down, obtain the PtFe nanometer electrical catalysts that carrying capacity is 60%, carrier is
C。
8th, non-loading type PtFe nanometer electrical catalysts are prepared, Pt and Fe mol ratio are 1:1.
(1) synthesis of metal carbonyl clusterses：It is Pt in molar ratio：Fe=1:1 ratio weighs compound containing platinum and chlorination
In methyl alcohol, stirring is to being completely dissolved for dissolved ferric iron；Sodium acetate and sodium hydroxide, control are added into the solution dissolved with metal ion
PH value of solution=8 processed；CO gas is passed through into reaction system again to remove in system after air, reacting 20h at 80 DEG C obtains
Metal carbonyl clusterses solution.
(2) template injection is sacrificed：In N2Or under CO gas shields, quantitative oxidation is added into metal carbonyl clusterses solution
Magnesium, continuing stirring makes magnesium oxide dispersion uniform.
(3) coreduction of metal cluster compound：Air is passed through after reaction system is cooled into 20 DEG C, the hydroboration that will have been configured
Sodium solution is added in reaction system, and sodium borohydride is 10 with metal ion mol ratio:1, continue filtration washing after reaction 18h,
Then 4h is dried at 60 DEG C.
(4) catalyst is heat-treated：By dried product exhibited in H2Under Ar mixed atmosphere, hot place is carried out in 500 DEG C of conditions
2h is managed, then passes to N230min, product is set to be taken out after cooling down.
(5) dissolving of template is sacrificed：Continue one section of stirring after a certain amount of sulfuric acid solution is added into the sample after cooling
Time, then dry, obtained as non-loading type PtFe nanometer electrical catalysts after filtration washing 5 times.
9th, carrying capacity is prepared as 60% PtNi/C loaded nano elctro-catalysts, and Pt and Ni mol ratio are 2:1.
(1) preparation of metal carbonyl clusterses solution：It is Pt in molar ratio：Ni=2:1 ratio weigh compound containing platinum and
Nickel acetate dissolves in methyl alcohol, and stirring is to being completely dissolved；Sodium acetate and hydroxide are added into the solution dissolved with metal ion
Sodium, control pH value of solution=13；CO gas is passed through into reaction system again, continues to obtain metal carbonyl in 60 DEG C of reaction 18h
Base cluster polymer solution.
(2) injection of carrier：Quantitative carbon black is added into solution, metal ladings is continued stirring for 60% makes it scattered equal
It is even.
(3) coreduction of metal cluster compound：Air is passed through after reaction system is cooled into 30 DEG C, the hydroboration that will have been configured
Sodium solution is added in reaction system, and sodium borohydride is 25 with metal ion mol ratio:1, continue filtration washing after reaction 24h,
Then 4h is dried at 60 DEG C.
(4) catalyst is heat-treated：By dried product exhibited in H2Under Ar mixed atmosphere, hot place is carried out in 800 DEG C of conditions
20h is managed, then passes to N230min, product is taken out after cooling down, obtain the PtNi nanometer electrical catalysts that carrying capacity is 60%, carrier
For C.Its XRD spectrum is shown in Fig. 8, and in Fig. 8, XRD spectrum shows 6 peaks, wherein being carbon peak at 23 ° or so of peak, remaining 5 peak is
Pt peak, (111), (200), (220), (311) and (222) crystal face is followed successively by from small to large, the oxidation peak and Ni without Ni
Oxide peak, and offset compared to the diffraction maximum of Pt simple substance to high position, show that Ni enters in Pt lattices, form Pt-Ni and close
Gold..
10th, non-loading type PtNi nanometer electrical catalysts are prepared, Pt and Ni mol ratio are 1:1.
(1) preparation of metal carbonyl clusterses solution：It is Pt in molar ratio：Ni=1:1 ratio weigh compound containing platinum and
Nickel acetate dissolves in methyl alcohol, and stirring is to being completely dissolved；Sodium acetate and hydroxide are added into the solution dissolved with metal ion
Sodium, control pH value of solution=8；CO gas is passed through into reaction system again to remove in system after air, reacts 20h at 80 DEG C
Obtain metal carbonyl clusterses solution.
(2) template injection is sacrificed：In N2Or under CO gas shields, quantitative oxidation is added into metal carbonyl clusterses solution
Magnesium carrier, continuing stirring makes magnesium oxide dispersion uniform.
(3) coreduction of metal cluster compound：Air is passed through after reaction system is cooled into 20 DEG C, the hydroboration that will have been configured
Sodium solution is added in reaction system, and sodium borohydride is 10 with Ni ions mol ratio:1, continue filtration washing after reaction 18h, so
Afterwards in 60 DEG C of dry 4h.
(4) catalyst is heat-treated：By dried product exhibited in H2Under Ar mixed atmosphere, hot place is carried out in 500 DEG C of conditions
After managing 2h, N is passed through230min makes product be taken out after cooling down.
(5) dissolving of template is sacrificed：Continue one section of stirring after a certain amount of sulfuric acid solution is added into the sample after cooling
Time, then dried after filtration washing 5 times, obtain non-loading type PtNi nanometer electrical catalysts.
11st, carrying capacity is prepared as 60% support type PtCr/C nanometer electrical catalysts, and Pt and Cr mol ratio are 2:1.
(1) synthesis of metal carbonyl clusterses：It is Pt in molar ratio：Cr=2:1 ratio weighs compound containing platinum and chlorination
Chromium dissolves in methyl alcohol, and stirring is to being completely dissolved；Sodium acetate and sodium hydroxide, control are added into the solution dissolved with metal ion
PH value of solution=13 processed；CO gas is passed through into reaction system again, continues to obtain the conjunction of metal-carbonyl cluster in 60 DEG C of reaction 18h
Thing solution.
(2) injection of carrier：Quantitative carbon black is added into solution, metal ladings is continued stirring for 60% makes it scattered equal
It is even.
(3) coreduction of metal cluster compound：Air is passed through after reaction system is cooled into 30 DEG C, the hydroboration that will have been configured
Sodium solution is added in reaction system, and sodium borohydride is 25 with Cr ions mol ratio:1, continue filtration washing after reaction 24h, so
Afterwards in 60 DEG C of dry 4h.
(4) catalyst is heat-treated：By dried product exhibited in H2It is heat-treated with Ar mixed atmospheres in 800 DEG C of conditions
N is passed through after 20h230min, product is taken out after cooling down, obtain the PtCr nanometer electrical catalysts that carrying capacity is 60%, carrier C.
12nd, non-loading type PtCr nanometer electrical catalysts are prepared, Pt and Cr mol ratio are 1:1.
(1) synthesis of catalyst precursor metal carbonyl clusterses：It is Pt in molar ratio：Cr=1:1 ratio weighs platiniferous
In methyl alcohol, stirring is to being completely dissolved for compound and chromium chloride dissolving；Sodium acetate is added into the solution dissolved with metal ion
And sodium hydroxide, control pH value of solution=8；CO gas is passed through into reaction system again to remove in system after air, 80
DEG C reaction 20h obtain metal carbonyl clusterses solution.
(2) template injection is sacrificed：In N2Or under CO gas shields, quantitative oxidation is added into metal carbonyl clusterses solution
Magnesium, continuing stirring makes magnesium oxide dispersion uniform.
(3) coreduction of metal cluster compound：Air is passed through after reaction system is cooled into 20 DEG C, the hydroboration that will have been configured
Sodium solution is added in reaction system, and sodium borohydride is 10 with Cr ions mol ratio:1, continue filtration washing after reaction 18h, so
4h is dried at 60 DEG C afterwards.
(4) catalyst is heat-treated：By dried product exhibited in H2Under Ar mixed atmosphere, hot place is carried out in 500 DEG C of conditions
N is passed through after reason 2h230min, product is set to be taken out after cooling down.
(5) dissolving of template is sacrificed：Continue one section of stirring after a certain amount of sulfuric acid solution is added into the sample after cooling
Time, then dried after filtration washing 5 times, obtain non-loading type PtCr nanometer electrical catalysts.
13rd, carrying capacity is prepared as 60% PtCu/C nanometer electrical catalysts, and Pt and Cu mol ratio are 2:1.
(1) preparation of metal carbonyl clusterses solution：It is Pt in molar ratio：Cu=2:1 ratio weigh compound containing platinum and
Copper chloride dissolves in methyl alcohol, and stirring is to being completely dissolved；Sodium acetate and hydroxide are added into the solution dissolved with metal ion
Sodium, control pH value of solution=13；CO gas is passed through into reaction system again, continues to obtain metal carbonyl in 60 DEG C of reaction 18h
Base cluster polymer solution.
(2) injection of carrier：Quantitative carbon black is added into solution, it is 60% to make metal ladings, and continuing stirring makes it scattered
Uniformly.
(3) coreduction of metal cluster compound：Air is passed through after reaction system is cooled into 30 DEG C, the hydroboration that will have been configured
Sodium solution is added in reaction system, and the mol ratio of sodium borohydride and Cu ions is 25:1, continue filtration washing after reaction 24h,
Then in 60 DEG C of dry 4h.
(4) catalyst is heat-treated：By dried product exhibited in H2Under Ar mixed atmosphere, hot place is carried out in 800 DEG C of conditions
After managing 20h, N is passed through230min, product is taken out after cooling down, obtain the PtCu nanometer electrical catalysts that carrying capacity is 60%, carrier is
C。
14th, unsupported PtCu nanometer electrical catalysts are prepared, Pt and Cu mol ratio are 1:1.
(1) preparation of metal carbonyl clusterses solution：It is Pt in molar ratio：Cu=1:1 ratio weigh compound containing platinum and
Copper chloride dissolves in methyl alcohol, and stirring is to being completely dissolved；Sodium acetate and hydroxide are added into the solution dissolved with metal ion
Sodium, control pH value of solution=8；CO gas is passed through into reaction system again to remove in system after air, reacts 20h at 80 DEG C
Obtain metal carbonyl clusterses solution.
(2) template injection is sacrificed：In N2Or under CO gas shields, quantitative oxidation is added into metal carbonyl clusterses solution
Magnesium, continuing stirring makes magnesium oxide dispersion uniform.
(3) coreduction of metal cluster compound：Air is passed through after reaction system is cooled into 20 DEG C, the hydroboration that will have been configured
Sodium solution is added in reaction system, and sodium borohydride is 10 with Cu ions mol ratio:1, continue filtration washing after reaction 18h, so
4h is dried at 60 DEG C afterwards.
(4) catalyst is heat-treated：By dried product exhibited in H2Under Ar mixed atmosphere, hot place is carried out in 500 DEG C of conditions
2h is managed, then passes to N230min, product is set to be taken out after cooling down.
(5) dissolving of template is sacrificed：Continue one section of stirring after a certain amount of sulfuric acid solution is added into the sample after cooling
Time, then dried after filtration washing 5 times, obtain non-loading type PtCu nanometer electrical catalysts.
15th, carrying capacity is prepared as 60% Pt Pd/C nanometer electrical catalysts, and Pt and Pd mol ratio are 2:1.
(1) preparation of metal carbonyl clusterses solution：It is Pt in molar ratio：Pd=2:1 ratio weigh compound containing platinum and
Palladium bichloride dissolves in methyl alcohol, and stirring is to being completely dissolved；Sodium acetate and hydroxide are added into the solution dissolved with metal ion
Sodium, control pH value of solution=13；CO gas is passed through into reaction system again, continues to react 18h at 60 DEG C, obtains metal carbonyl
Base cluster polymer solution.
(2) injection of carrier：Quantitative carbon black is added into solution, it is 60% to make metal ladings, and continuing stirring makes it scattered
Uniformly.
(3) coreduction of metal cluster compound：Air is passed through after reaction system is cooled into 30 DEG C, the hydroboration that will have been configured
Sodium solution is added in reaction system, and sodium borohydride is 25 with Pd ions mol ratio:1, continue filtration washing after reaction 24h, so
4h is dried under the conditions of 60 DEG C afterwards.
(4) catalyst is heat-treated：By dried product exhibited in H2Under Ar mixed atmospheres, it is heat-treated in 800 DEG C of conditions
20h, then pass to N230min, product is taken out after cooling down, obtain the PtPd nanometer electrical catalysts that carrying capacity is 60%, carrier is
C。
16th, non-loading type Pt Pd nanometer electrical catalysts are prepared, Pt and Pd mol ratio are 1:1.
(1) preparation of metal carbonyl clusterses solution：It is Pt in molar ratio：Pd=1:1 ratio weigh compound containing platinum and
Palladium bichloride, in methyl alcohol, stirring is to being completely dissolved for dissolving；Sodium acetate and hydroxide are added into the solution dissolved with metal ion
Sodium, control pH value of solution=8；CO gas is passed through into reaction system again to remove in system after air, reacts 20h at 80 DEG C
Obtain metal carbonyl clusterses solution.
(2) template injection is sacrificed：In N2Or under CO gas shields, quantitative oxidation is added into metal carbonyl clusterses solution
Magnesium carrier, continuing stirring makes magnesium oxide dispersion uniform.
(3) coreduction of metal cluster compound：Air is passed through after reaction system is cooled into 20 DEG C, the hydroboration that will have been configured
Sodium solution is added in reaction system, and sodium borohydride is 10 with Pd ions mol ratio:1, continue filtration washing after reaction 18h, so
60 DEG C of dry 4h afterwards.
(4) catalyst is heat-treated：By dried product exhibited in H2Under Ar mixed atmosphere, hot place is carried out in 500 DEG C of conditions
After managing 2h, N is passed through230min, product is set to be taken out after cooling down.
(5) dissolving of template is sacrificed：Continue one section of stirring after a certain amount of sulfuric acid solution is added into the sample after cooling
Time, then dry, obtained as non-loading type PtPd nanometer electrical catalysts after filtration washing 8 times.
17th, carrying capacity is prepared as 60% Pt Ag/C nanometer electrical catalysts, and Pt and Ag mol ratio are 2:1.
(1) synthesis of metal carbonyl clusterses solution：It is Pt in molar ratio：Ag=2:1 ratio weigh compound containing platinum and
Silver chlorate dissolves in methyl alcohol, and stirring is to being completely dissolved；Sodium acetate and hydroxide are added into the solution dissolved with metal ion
Sodium, control pH value of solution=13；CO gas is passed through into reaction system again, continues to react 18h at 60 DEG C, obtains metal carbonyl
Base cluster polymer solution.
(2) injection of carrier：Quantitative carbon black is added into solution, it is 60% to make metal ladings, and continuing stirring makes it scattered
Uniformly.
(3) coreduction of metal cluster compound：Air is passed through after reaction system is cooled into 30 DEG C, the hydroboration that will have been configured
Sodium solution is added in reaction system, and sodium borohydride is 25 with Ag ions mol ratio:1, continue filtration washing after reaction 24h, so
60 DEG C of dry 4h afterwards.
(4) catalyst is heat-treated：By dried product exhibited in H2Under Ar mixed atmosphere, hot place is carried out in 800 DEG C of conditions
20h is managed, then passes to N230min, product is taken out after cooling down, obtain the PtAg nanometer electrical catalysts that carrying capacity is 60%, carrier
For C.
Embodiment 18, prepare non-loading type PtAg nanometer electrical catalysts, Pt and Ag mol ratio are 1:1.
(1) preparation of metal carbonyl clusterses solution：It is Pt in molar ratio：Ag=1:1 ratio weigh compound containing platinum and
Silver chlorate dissolves in methyl alcohol, and stirring is to being completely dissolved；Sodium acetate and hydroxide are added into the solution dissolved with metal ion
Sodium, control pH value of solution=8；CO gas is passed through into reaction system again to remove in system after air, reacts 20h at 80 DEG C
Obtain metal carbonyl clusterses solution.
(2) template injection is sacrificed：In N2Or under CO gas shields, quantitative oxidation is added into metal carbonyl clusterses solution
Magnesium, continuing stirring makes magnesium oxide dispersion uniform.
(3) coreduction of metal cluster compound：Air is passed through after reaction system is cooled into 20 DEG C, the hydroboration that will have been configured
Sodium solution is added in reaction system, and sodium borohydride is 10 with Ag ions mol ratio:1, continue filtration washing after reaction 18h, so
4h is dried under the conditions of 60 DEG C afterwards.
(4) catalyst is heat-treated：By dried product exhibited in H2Under Ar mixed atmosphere, hot place is carried out in 500 DEG C of conditions
2h is managed, then passes to N230min, product is set to be taken out after cooling down.
(5) dissolving of template is sacrificed：Continue one section of stirring after a certain amount of sulfuric acid solution is added into the sample after cooling
Time, then dried after filtration washing 5 times, obtain non-loading type PtAg nanometer electrical catalysts.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be regarded as
Protection scope of the present invention.
Claims (8)
- A kind of 1. preparation method of nanometer electrical catalyst, it is characterised in that including：Metal carbonyl clusterses solution is provided, the metal carbonyl clusterses include platinum and the first metal；Carrier is added into the metal carbonyl clusterses solution or sacrifices template to adjust the carrying capacity of the platinum and the first metal, Total carrying capacity of platinum and the first metal is adjusted to 20%~100%；Oxidizing gas is passed through into the metal carbonyl clusterses solution, and adds reducing agent, is reacted, the oxidisability Gas includes one kind in air, oxygen or ozone, and the reducing agent includes：In sodium borohydride, hydrazine hydrate and ascorbic acid One kind；Reacted product is dried；Dried product exhibited is heat-treated.
- 2. the preparation method of nanometer electrical catalyst according to claim 1, it is characterised in that described when being reacted, gold The temperature for belonging to Carbonyl Clusters solution is 20 DEG C~100 DEG C, and the mol ratio of reducing agent and the first metal is 5~25:1.
- 3. the preparation method of nanometer electrical catalyst according to claim 1, it is characterised in that first metal be Fe, One kind in Co, Ni, Cr, Cu, Ru, Pd and Ag.
- 4. the preparation method of nanometer electrical catalyst according to claim 1, it is characterised in that prepare metal carbonyl clusterses The method of solution includes：Dissolve to form solution by compound containing platinum and containing the first metallic compound；Sodium acetate and sodium hydroxide are added into the solution, to adjust the pH value of the solution as 7~13；Carbon monoxide is passed through into the solution, it is 20 DEG C~80 DEG C to keep solution temperature, is maintained 2 hours~24 hours.
- 5. the preparation method of nanometer electrical catalyst according to claim 1, it is characterised in that the material of the carrier includes At least one of carbon black, graphene, CNT and mesoporous carbon；The sacrifice mould material includes nano magnesia, nanometer At least one of aluminum oxide and nano zine oxide.
- 6. the preparation method of nanometer electrical catalyst according to claim 5, it is characterised in that also include：Product after heat treated adds acid solution, to remove the sacrifice template.
- 7. the preparation method of nanometer electrical catalyst according to claim 6, it is characterised in that the acid solution be sulfuric acid, One kind in hydrochloric acid, nitric acid and perchloric acid.
- 8. the preparation method of nanometer electrical catalyst according to claim 1, it is characterised in that the temperature of the heat treatment is 100 DEG C~800 DEG C, the time is 2 hours~20 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007272A (en) * | 2006-12-01 | 2007-08-01 | 中国科学院上海微系统与信息技术研究所 | Preparation method of platinum nanoparticle electrocatalyst based on metal cluster approach |
| CN101015798A (en) * | 2007-02-16 | 2007-08-15 | 中国科学院上海微系统与信息技术研究所 | Platinum-ruthenium radical nano-electrocatalyst and preparing method based on metal cluster compound path |
| CN102794171A (en) * | 2012-06-28 | 2012-11-28 | 上海中科高等研究院 | Method for preparing platinum black/ platinum ruthenium black nano electro-catalyst by using sacrificial magnesia carrier |
| CN103657649A (en) * | 2013-12-27 | 2014-03-26 | 中国科学院上海高等研究院 | Method for preparing carbon-supported nano-platinum-chromium intermetallic compound serving as cathode catalyst of proton exchange membrane fuel cell |
-
2016
- 2016-06-17 CN CN201610445365.4A patent/CN105932308B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007272A (en) * | 2006-12-01 | 2007-08-01 | 中国科学院上海微系统与信息技术研究所 | Preparation method of platinum nanoparticle electrocatalyst based on metal cluster approach |
| CN101015798A (en) * | 2007-02-16 | 2007-08-15 | 中国科学院上海微系统与信息技术研究所 | Platinum-ruthenium radical nano-electrocatalyst and preparing method based on metal cluster compound path |
| CN102794171A (en) * | 2012-06-28 | 2012-11-28 | 上海中科高等研究院 | Method for preparing platinum black/ platinum ruthenium black nano electro-catalyst by using sacrificial magnesia carrier |
| CN103657649A (en) * | 2013-12-27 | 2014-03-26 | 中国科学院上海高等研究院 | Method for preparing carbon-supported nano-platinum-chromium intermetallic compound serving as cathode catalyst of proton exchange membrane fuel cell |
Non-Patent Citations (1)
| Title |
|---|
| "Electrocatalytic Oxidation of Formic Acid on Pd/Ni Heterostructured Catalyst";Mingjun Ren et al;《电化学》;20121231;第18卷(第6期);第515-520页 * |
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