CN105932308A - Preparation method for nanometer electrocatalyst - Google Patents
Preparation method for nanometer electrocatalyst Download PDFInfo
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- CN105932308A CN105932308A CN201610445365.4A CN201610445365A CN105932308A CN 105932308 A CN105932308 A CN 105932308A CN 201610445365 A CN201610445365 A CN 201610445365A CN 105932308 A CN105932308 A CN 105932308A
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- H—ELECTRICITY
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Abstract
Disclosed is a preparation method for a nanometer electrocatalyst. The preparation method comprises the steps of providing a metal carbonyl cluster compound solution, wherein the metal carbonyl cluster compound solution comprises platinum and first metal; adjusting the carrying capacity of platinum and first metal in the metal carbonyl cluster compound solution into 20-100%; pumping an oxidizing gas into the metal carbonyl cluster compound solution and adding a reducing agent to be reacted; drying the reacted product; and carrying out thermal treatment on the dried product. By adoption of the preparation method, the high-performance nanometer electrocatalyst with small grain diameter and controllable components can be prepared.
Description
Technical field
The present invention relates to eelctro-catalyst field, particularly relate to the preparation method of a kind 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, its
Having energy conversion efficiency high, easily start, the advantage such as pollution-free is it is considered to be one of following optimal energy.
But, the widely used eelctro-catalyst of fuel cell is Pt sill.Owing to platinum scarcity of resources, price are held high
Expensive, cause fuel cell cost to remain high, one of obstacle becoming commercializing fuel cells.In order to reduce
Fuel cell cost, one of effective strategy is material nano, promotes the utilization rate of material to greatest extent,
It is simultaneously introduced binary metal in Pt lattice, forms alloy with Pt.Due to the binary metal unit introduced
Structure effect, electronic effect and ligand effect is formed, it is possible to strengthen Pt catalysis between element atom and Pt atom
The electrocatalysis characteristics such as antitoxinization performance, electro catalytic activity and the durability of agent.
The electrocatalysis characteristic of catalyst is closely related with itself particle size, composition, structure and pattern.Example
As, atomic ratio is 1:1, has the Pt-Ru alloy of small particle, is considered owing to having difunctional effect
It is the catalyst best to anodic oxidation of methanol；Pt-Co, the Pt-Ni catalyst catalysis to oxygen reduction activity
Performance is that report is the highest at present.It addition, Proton Exchange Membrane Fuel Cells is in actual application, for carrying
High inside battery reactant, product and the transmission of intermediate product, reduce the internal resistance of cell, generally require use
The catalyst that metal ladings is high, wherein metal quality mark wt >=50%, but in preparation process, high
Metal ladings would generally make metal nanoparticle reunite or condensation growth, thus causes the specific activity of catalyst
Surface area declines, and causes the utilization rate of Pt material to reduce.
Therefore, how to obtain that metal ladings is high, particle diameter is little, it is controlled to form, pattern is homogeneous, can scale system
Standby nanometer electrical catalyst is one of challenge of research.With surfactant more than current document report, stablize
Agent is the auxiliary preparation carrying capacity nanometer electrical catalyst less than 40wt%, causes the biggest in actual production and application
Inconvenience, such as: the more difficult usual removal of surfactant, easily remain in nanoparticle surface, reduction is received
Rice eelctro-catalyst performance.
So, the preparation method of nanometer electrical catalyst needs further to be improved, and to be formed, particle diameter is little and electricity is urged
Change the nanometer electrical catalyst that performance is high.
Summary of the invention
The technical problem to be solved is to provide the preparation method of a kind of Nanoalloy eelctro-catalyst.
In order to solve the problems referred to above, the invention provides the preparation method of a kind of Nanoalloy eelctro-catalyst, bag
Include: providing metal carbonyl clusters solution, described metal carbonyl clusters comprises platinum and the first metal；By institute
State the carrying capacity of platinum and the first metal in metal carbonyl clusters and be adjusted to 20%～100%；To described metal-carbonyl
Cluster compound solution is passed through oxidizing gas, and adds reducing agent, react；Reacted product is done
Dry；Dried product exhibited is heat-treated.
Optionally, described in when reacting, the temperature of metal carbonyl clusters solution is 20 DEG C～100 DEG C,
The mol ratio of reducing agent and the first metal is 5～25:1.
Optionally, described first metal is in Fe, Co, Ni, Cr, Cu, Ru, Pd and Ag
Kind.
Optionally, the method preparing metal carbonyl clusters solution includes: will contain platinum compounds and containing the first gold medal
Belong to compound and dissolve formation solution；Sodium acetate and NaOH is added in described solution, described molten to regulate
The pH value of liquid is 7～13；Being passed through carbon monoxide in described solution, keeping solution temperature is 20 DEG C～80 DEG C,
Maintain 2 hours～24 hours.
Optionally, in described metal carbonyl clusters solution, add carrier or sacrifice template adjusts described gold
Belong to platinum and the carrying capacity of the first metal in Carbonyl Clusters.
Optionally, during the material of described carrier includes carbon black, Graphene, CNT and mesoporous carbon extremely
Few one；Described sacrificial mold plate material includes in nano magnesia, nano aluminium oxide and nano zine oxide
At least one.
Optionally, also include: the product after heat treated adds acid solution, to remove described sacrifice template.
Optionally, the one during described acid solution is sulfuric acid, hydrochloric acid, nitric acid and perchloric acid.
Optionally, described reducing agent includes: the one in sodium borohydride, hydrazine hydrate and ascorbic acid.
Optionally, the temperature of described heat treatment is 100 DEG C～800 DEG C, and the time is 2 hours～20 hours.
The present invention is by preparing metal carbonyl clusters as catalyst precursors, and by carrier or sacrificial mold
Plate adjusts after metal ladings, and metal carbonyl clusters is carried out coreduction and heat treatment, it is thus achieved that particle diameter is little,
Form controlled eelctro-catalyst, course of reaction need not surfactant and participate in, such that it is able to improve preparation
The performance of the nanometer electrical catalyst obtained.
Accompanying drawing explanation
Fig. 1 is the flow chart of the preparation method of the nanometer electrical catalyst of the detailed description of the invention of the present invention；
Fig. 2 be the load prepared in the detailed description of the invention of the present invention be the PtCo of 40% for C, carrying capacity
The X ray diffracting spectrum of nanometer electrical catalyst；
Fig. 3 be the load prepared in the detailed description of the invention of the present invention be the PtCo of 40% for C, carrying capacity
The transmission electron microscope photo of nanometer electrical catalyst；
Fig. 4 be the load prepared in the detailed description of the invention of the present invention be the PtCo of 70% for C, carrying capacity
The transmission electron microscope photo of nanometer electrical catalyst；
Fig. 5 be the load prepared in the detailed description of the invention of the present invention be the PtCo of 70% for C, carrying capacity
The X ray diffracting spectrum of nanometer electrical catalyst；
Fig. 6 be the load prepared in the detailed description of the invention of the present invention be the PtRu of 20% for C, carrying capacity
The transmission electron microscope photo of nanometer electrical catalyst；
Fig. 7 is the non-loaded PtRu nanometer electrical catalyst prepared in the detailed description of the invention of the present invention
X ray diffracting spectrum；
Fig. 8 be the load prepared in the detailed description of the invention of the present invention be the PtNi of 60% for C, carrying capacity
The X ray diffracting spectrum of nanometer electrical catalyst.
Detailed description of the invention
The detailed description of the invention of preparation method to the nanometer electrical catalyst that the present invention provides below in conjunction with the accompanying drawings
Elaborate.
Refer to Fig. 1, for the schematic flow sheet of preparation method of the nanometer electrical catalyst of the present invention.
Step S101: prepare metal carbonyl clusters solution, described metal carbonyl clusters comprises platinum and
One metal.
The methods such as redox, redox condensation and thermal condensation can be used to form described metal-carbonyl bunch close
Thing solution.
As a specific embodiment of the present invention, the method preparing metal carbonyl clusters solution includes:
Platinum compounds will be contained and dissolve formation solution containing the first metallic compound；In described solution add sodium acetate and
NaOH, is 7～13 to regulate the pH value of described mixed solution；It is passed through carbon monoxide in described solution,
Keeping solution temperature is 20 DEG C～80 DEG C, maintains 2 hours～24 hours, obtains described metal carbonyl clusters
Solution.
Weigh described containing platinum compounds with containing after the first metallic compound according to target composition, be dissolved in methyl alcohol,
In nitrile or toluene solution, stirring, to being completely dissolved, forms described mixed solution.
Concrete, described include containing platinum compounds: platinic sodium chloride, chloroplatinic acid, potassium chloroplatinate, ammonium chloroplatinate,
First metal can be the one in Fe, Co, Ni, Cr, Cu, Ru, Pd and Ag.Described first
Metallic atom can form alloy with pt atom, has structure effect, electronic effect and ligand effect, it is possible to
Strengthen platinum catalyst performance.
Described first metallic compound that contains includes: cobalt chloride, ruthenic chloride, iron chloride, nickel acetate, chromium chloride,
Copper chloride, palladium bichloride or silver chlorate etc..
Described metal carbonyl clusters is as the presoma of nanometer electrical catalyst to be prepared.
Step S102: the carrying capacity of platinum and the first metal in described metal carbonyl clusters is adjusted to
20%～100%.
Can adjust described by adding carrier or sacrifice template in described metal carbonyl clusters solution
Platinum and the carrying capacity of the first metal in metal carbonyl clusters so that in metal carbonyl clusters, described platinum and
The mass fraction of one metal is 20%～100%, i.e. carrying capacity is 20%～100%.Add carrier or sacrifice template
Rear stirring so that it is be uniformly dispersed.
The material of described carrier can include at least one in carbon black, Graphene, CNT and mesoporous carbon.
Described carrier can also play space obstacle effect in subsequent heat treatment, it is to avoid nanometer agglomeration occurs.
Described sacrificial mold plate material includes at least in nano magnesia, nano aluminium oxide and nano zine oxide
Kind.
Step S103: be passed through oxidizing gas in described metal carbonyl clusters solution, and add reduction
Agent, reacts.
Concrete, in course of reaction, described metal carbonyl clusters solution temperature can be adjusted to 20 DEG C
～the arbitrary temperature in 100 DEG C, can be adjusted by adjustment metal carbonyl clusters solution temperature and ultimately form
The particle size of nanometer electrical catalyst.
Described oxidizing gas can be air, oxygen or O3Deng, by described oxidizing gas by carbonyl
Platinum oxidation, forms Pt atom.
Described reducing agent can be the material that sodium borohydride, hydrazine hydrate or ascorbic acid etc. have reproducibility, uses
In the first reducing metal ions in solution is formed atom or metallic state.Described reducing agent can dissolve after shape
Reductant solution is become to add in described metal carbonyl clusters solution.
The mol ratio of described reducing agent and the first metal can be 5～25:1, can be by adjusting described reducing agent
With the particle size that the mol ratio of the first metal adjusts the nanometer electrical catalyst ultimately formed.
As a specific embodiment of the present invention, the time of described reaction is 8 hours～24 hours.
Step S104: reacted product is dried.
Such as: be dried 4 hours in the environment of 60 DEG C, it is thus achieved that dried product exhibited.
Step S105: dried product exhibited is heat-treated.
As a specific embodiment of the present invention, described heat treatment is entered under reducing atmosphere or inert atmosphere
OK, it is to avoid product reacts with environmental gas, described reducing atmosphere can be H2, described inert atmosphere
Can be Ar, He, Ne or N2, it is also possible to include reducing atmosphere and inert atmosphere simultaneously.The temperature being heat-treated
Degree is 100 DEG C～800 DEG C, and the time is 2 hours～20 hours, after heat treatment, can be passed through nitrogen to enter
Row cooling, such as, be passed through nitrogen 30～50 minutes.
Described heat treatment is for forming the alloy nano eelctro-catalyst of platinum and the first metal, and it is possible to remove
The impurity such as the oxide of described nanometer electrical catalyst particle surface, hydroxy compounds.
In the detailed description of the invention of the present invention, if in step S102, adjust by adding sacrifice template
Platinum and the carrying capacity of the first metal in metal carbonyl clusters, then after being heat-treated, in addition it is also necessary to thermotropism
Product after process adds acid solution, to remove described sacrifice template.
Described acid solution can be the one in sulfuric acid, hydrochloric acid, nitric acid and perchloric acid.
Follow-up the catalyst obtained such as can also be carried out, filter and be dried at the process, to remove catalyst
In foreign ion, such as halogen ion.
The high-performance nano alloy electricity that can prepare particle diameter according to the method described above controlled less than 5nm, composition is urged
Agent.
Below for using said method to prepare multiple detailed description of the invention of nanometer electrical catalyst.
1, the loaded nano eelctro-catalyst of the PtCo/C that carrying capacity is 40%, the mol ratio of Pt Yu Co are prepared
For 1:1.
Concrete grammar includes: the preparation of (1) metal carbonyl clusters solution: in molar ratio for Pt:Co=1:1
Ratio weighs and is dissolved in methyl alcohol containing platinic sodium chloride and cobalt chloride, and stirring, to being completely dissolved, forms mixed solution；
In the described mixed solution being dissolved with metal ion, add sodium acetate and NaOH, control pH value of solution=7；
In reaction system, it is passed through CO gas again, keeps 20 DEG C to react 2 hours, obtain metal-carbonyl bunch and close
Thing solution.
(2) injection of carrier: add quantitative carbon black in solution, the carrying capacity adjusting Pt Yu Co is 40%,
Continuing stirring makes it be uniformly dispersed.
(3) coreduction of metal cluster compound: keeping reaction temperature is 20 DEG C, is passed through air, by configuration well
Sodium borohydride solution join in reaction system, sodium borohydride and Co ion mol ratio are 5:1, continue anti-
After answering 8h, filtration washing, then it is dried 4 hours at 60 DEG C.
(4) catalyst is heat-treated: by dried product exhibited at H2With under the mixed atmosphere of Ar, at 100 DEG C
Condition carries out being heat-treated 2 hours, then passes to N230 minutes, take out after making product cooling, it is thus achieved that carrying capacity
Being the PtCo loaded nano eelctro-catalyst of 40%, carrier is C.Its X ray diffracting spectrum and transmission electricity
Mirror collection of illustrative plates refer to Fig. 2, Fig. 3.In Fig. 2,6 peaks of XRD spectrum display, wherein at about 23 °
Peak is carbon peak, and remaining 5 peak is the peak of Pt, is followed successively by (111), (200), (220), (311) from small to large
And (222) crystal face, there is no the oxidation peak of Pt and the oxide peak of Co and Co, and compare Pt simple substance
Diffraction maximum offset to high position, show that Co enters in Pt lattice, form Pt-Co alloy.
2, preparation carrying capacity is the PtCo/C loaded nano eelctro-catalyst of 70%, and the mol ratio of Pt with Co is
2:1。
(1) preparation of metal carbonyl clusters solution: weigh platiniferous for Pt:Co=2:1 ratio in molar ratio
Compound and cobalt chloride are dissolved in methyl alcohol, and stirring is to being completely dissolved；In the solution being dissolved with metal ion
Add sodium acetate and NaOH, control pH value of solution=13；CO gas it is passed through again in reaction system,
Continue to react 18 hours at 60 DEG C, obtain metal carbonyl clusters solution.
(2) injection of carrier: add quantitative carbon black in solution, the carrying capacity making Pt Yu Co is 70%,
Continuing stirring makes it be uniformly dispersed.
(3) coreduction of metal cluster compound: be passed through air after reaction system is cooled to 30 DEG C, will configuration
Good sodium borohydride solution joins in reaction system, and sodium borohydride and Co ion mol ratio are 25:1, continue
Filtration washing after continuous reaction 24h, is then dried 4 hours at 60 DEG C.
(4) catalyst is heat-treated: by dried product exhibited at H2With under the mixed atmosphere of Ar, at 200 DEG C
Condition carries out being heat-treated 20 hours, then passes to N230 minutes, take out after making product cooling, it is thus achieved that carry
Amount is the PtCo nanometer electrical catalyst of 70%, loads as C, its transmission electron microscope (TEM) photo
Refer to Fig. 4, X-ray diffraction (XRD) collection of illustrative plates refer to Fig. 5, in Fig. 5, and XRD spectrum display 6
Individual peak, wherein the peak at about 23 ° is carbon peak, and remaining 5 peak is the peak of Pt, is followed successively by from small to large
(111), (200), (220), (311) and (222) crystal face, there is no oxidation peak and Co and Co of Pt
Oxide peak, and compare the diffraction maximum of Pt simple substance and offset to high position, show that Co enters Pt lattice
In, form Pt-Co alloy.
3, preparing non-loading type Pt-Co nanometer electrical catalyst, the mol ratio of Pt Yu Co is 1:1.
(1) preparation of metal carbonyl clusters solution: weigh platiniferous for Pt:Co=1:1 ratio in molar ratio
Compound and cobalt chloride are dissolved in methyl alcohol, and stirring is to being completely dissolved；In the solution being dissolved with metal ion
Add sodium acetate and NaOH, control pH value of solution=8；CO gas it is passed through again in reaction system
Remove in system after air, react 20 hours at 80 DEG C, obtain metal carbonyl clusters solution.
(2) sacrifice template to inject: at N2Or under CO gas shield, in metal carbonyl clusters solution
Add quantitative magnesia, continue stirring and make magnesium oxide dispersion uniform.
(3) coreduction of metal cluster compound: be passed through air after reaction system is cooled to 20 DEG C, will configuration
Good sodium borohydride solution joins in reaction system, and sodium borohydride and metal ion mol ratio are 10:1, continue
After continuous reaction 18 hours after filtration washing 60 DEG C be dried 4 hours.
(4) catalyst is heat-treated: by dried product exhibited at H2With under the mixed atmosphere of Ar, at 500 DEG C
Under the conditions of carry out being heat-treated 2 hours, then pass to N230 minutes, take out after making product cooling.
(5) dissolving of template is sacrificed: continue after the sample after cooling adds a certain amount of sulfuric acid solution
Stirring a period of time, then it is dried after filtration washing 5 times, i.e. obtains non-loading type Pt-Co nano electro-catalytic
Agent.
4, preparation carrying capacity is the PtRu/C loaded nano eelctro-catalyst of 20%, and the mol ratio of Pt with Ru is
1:1。
(1) preparation of metal carbonyl clusters: weigh containing chloroplatinic acid for Pt:Ru=1:1 ratio in molar ratio
Sodium and ruthenic chloride are dissolved in methyl alcohol, and stirring is to being completely dissolved；Add in the solution be dissolved with metal ion
Sodium acetate and NaOH, control pH value of solution=7；In reaction system, it is passed through CO gas again, protects
Hold 20 DEG C of reaction 2h and obtain many metal carbonyl clusterses solution.
(2) injection of carrier: add quantitative carbon black in solution, making metal ladings is 20%, continues to stir
Mix and make it be uniformly dispersed.
(3) coreduction of metal cluster compound: keeping reaction temperature is 20 DEG C, is passed through air, by configuration well
Sodium borohydride solution join in reaction system, sodium borohydride and Co ion mol ratio are 5:1, continue anti-
Answer after 8h 60 DEG C of dry 4h after filtration washing.
(4) catalyst is heat-treated: by dried product exhibited at H2With under Ar mixed atmosphere, at 100 DEG C of bars
After part carries out being heat-treated 2h, it is passed through N230min, takes out after making product cooling, it is thus achieved that carrying capacity is 20%
Pt Ru Nanoalloy eelctro-catalyst, carrier is C.Its transmission electron microscope picture is shown in Fig. 6.
5, preparation carrying capacity is the PtRu/C nanometer electrical catalyst of 60%, and the mol ratio of Pt Yu Ru is 2:1.
(1) preparation of metal carbonyl clusters solution: weigh platiniferous for Pt:Ru=2:1 ratio in molar ratio
Compound and ruthenic chloride are dissolved in methyl alcohol, and stirring is to being completely dissolved；In the solution being dissolved with metal ion
Add sodium acetate and NaOH, control pH value of solution=13；CO gas it is passed through again in reaction system,
Continue to obtain many metal carbonyl clusterses solution at 60 DEG C of reaction 18h.
(2) injection of carrier: add quantitative carbon black in solution, the carrying capacity making Pt Yu Ru is 60%,
Continuing stirring makes it be uniformly dispersed.
(3) coreduction of metal cluster compound: be passed through air after reaction system is cooled to 30 DEG C, will configuration
Good sodium borohydride solution joins in reaction system, and sodium borohydride and metal ion mol ratio are 25:1, continue
60 DEG C of dry 4h after filtration washing after continuous reaction 24h.
(4) catalyst is heat-treated: by dried product exhibited at H2With under Ar mixed atmosphere, at 800 DEG C of bars
After part carries out being heat-treated 20h, it is passed through N230min, takes out after making product cooling, it is thus achieved that carrying capacity is 60%
PtRu Nanoalloy eelctro-catalyst, carrier is C.
6, preparing non-loading type PtRu nanometer electrical catalyst, the mol ratio of Pt Yu Ru is 1:1.
(1) preparation of metal carbonyl clusters solution: weigh platiniferous for Pt:Ru=1:1 ratio in molar ratio
Compound and ruthenic chloride are dissolved in methyl alcohol, and stirring is to being completely dissolved；In the solution being dissolved with metal ion
Add sodium acetate and NaOH, control pH value of solution=8；CO gas it is passed through again in reaction system
Remove in system after air, obtain metal carbonyl clusters solution at 80 DEG C of reaction 20h.
(2) sacrifice template to inject: at N2Or under CO gas shield, in metal carbonyl clusters solution
Add quantitative magnesia, continue stirring and make magnesium oxide dispersion uniform.
(3) coreduction of metal cluster compound: be passed through air after reaction system is cooled to 20 DEG C, will configuration
Good sodium borohydride solution joins in reaction system, and sodium borohydride and Ru ion mol ratio are 10:1, continue
Filtration washing after continuous reaction 18h, is dried 4h under 60 DEG C of environment.
(4) catalyst is heat-treated: by dried product exhibited at H2With under the mixed atmosphere of Ar, at 500 DEG C
Condition carries out being heat-treated 2h, then passes to N230min, takes out after making product cooling.
(5) dissolving of magnesia: continue to stir after adding a certain amount of sulfuric acid solution in the sample after cooling
Mix a period of time, be then dried after filtration washing 5 times, it is thus achieved that non-loading type PtRu nanometer electrical catalyst.
Fig. 7 is shown in by its X-ray collection of illustrative plates, in Fig. 7, and 5 peaks of XRD spectrum display, described 5 peaks are the peak of Pt,
It is followed successively by (111), (200), (220), (311) and (222) crystal face from small to large, there is no the oxygen of Pt
Change peak and the oxide peak of Ru and Ru, and the diffraction maximum comparing Pt simple substance offsets to high position, shows
Ru enters in Pt lattice, forms Pt-Ru alloy.
7, preparation carrying capacity is the PtFe/C loaded nano eelctro-catalyst of 60%, and the mol ratio of Pt with Fe is
2:1。
(1) preparation of metal carbonyl clusters solution: weigh platiniferous for Pt:Fe=2:1 ratio in molar ratio
Compound and iron chloride are dissolved in methyl alcohol, and stirring is to being completely dissolved；In the solution being dissolved with metal ion
Add sodium acetate and NaOH, control pH value of solution=13；CO gas it is passed through again in reaction system,
Continue to obtain metal carbonyl clusters solution at 60 DEG C of reaction 18h.
(2) injection of carrier: add quantitative carbon black in solution, making metal ladings is 60%, continues to stir
Mix and make it be uniformly dispersed.
(3) coreduction of metal cluster compound: be passed through air after reaction system is cooled to 30 DEG C, will configuration
Good sodium borohydride solution joins in reaction system, and sodium borohydride and Fe ion mol ratio are 25:1, continue
60 DEG C of dry 4h after filtration washing after continuous reaction 24h.
(4) catalyst is heat-treated: by dried product exhibited at H2With under Ar mixed atmosphere 800 DEG C of conditions
Carry out being heat-treated 20h, then pass to N230min, takes out after making product cooling, it is thus achieved that carrying capacity is 60%
PtFe nanometer electrical catalyst, carrier is C.
8, preparing non-loading type PtFe nanometer electrical catalyst, the mol ratio of Pt and Fe is 1:1.
(1) synthesis of metal carbonyl clusters: weigh platiniferous chemical combination for Pt:Fe=1:1 ratio in molar ratio
Thing and iron chloride are dissolved in methyl alcohol, and stirring is to being completely dissolved；Add in the solution be dissolved with metal ion
Sodium acetate and NaOH, control pH value of solution=8；In reaction system, it is passed through CO gas again remove
In system after air, obtain metal carbonyl clusters solution at 80 DEG C of reaction 20h.
(2) sacrifice template to inject: at N2Or under CO gas shield, in metal carbonyl clusters solution
Add quantitative magnesia, continue stirring and make magnesium oxide dispersion uniform.
(3) coreduction of metal cluster compound: be passed through air after reaction system is cooled to 20 DEG C, will configuration
Good sodium borohydride solution joins in reaction system, and sodium borohydride and metal ion mol ratio are 10:1, continue
Filtration washing after continuous reaction 18h, is then dried 4h at 60 DEG C.
(4) catalyst is heat-treated: by dried product exhibited at H2With under the mixed atmosphere of Ar, at 500 DEG C
Condition carries out being heat-treated 2h, then passes to N230min, takes out after making product cooling.
(5) dissolving of template is sacrificed: continue after the sample after cooling adds a certain amount of sulfuric acid solution
Stirring a period of time, then it is dried after filtration washing 5 times, it is thus achieved that for non-loading type PtFe nano electro-catalytic
Agent.
9, preparation carrying capacity is the PtNi/C loaded nano eelctro-catalyst of 60%, and the mol ratio of Pt with Ni is
2:1。
(1) preparation of metal carbonyl clusters solution: weigh platiniferous for Pt:Ni=2:1 ratio in molar ratio
Compound and nickel acetate are dissolved in methyl alcohol, and stirring is to being completely dissolved；In the solution being dissolved with metal ion
Add sodium acetate and NaOH, control pH value of solution=13；CO gas it is passed through again in reaction system,
Continue to obtain metal carbonyl clusters solution at 60 DEG C of reaction 18h.
(2) injection of carrier: add quantitative carbon black in solution, making metal ladings is 60% continuation stirring
Make it be uniformly dispersed.
(3) coreduction of metal cluster compound: be passed through air after reaction system is cooled to 30 DEG C, will configuration
Good sodium borohydride solution joins in reaction system, and sodium borohydride and metal ion mol ratio are 25:1, continue
Filtration washing after continuous reaction 24h, is then dried 4h at 60 DEG C.
(4) catalyst is heat-treated: by dried product exhibited at H2With under the mixed atmosphere of Ar, at 800 DEG C
Condition carries out being heat-treated 20h, then passes to N230min, takes out after making product cooling, it is thus achieved that carrying capacity is 60%
PtNi nanometer electrical catalyst, carrier is C.Its XRD spectrum is shown in Fig. 8, and in Fig. 8, XRD spectrum is aobvious
Showing 6 peaks, wherein the peak at about 23 ° is carbon peak, and remaining 5 peak is the peak of Pt, depends on from small to large
Secondary is (111), (200), (220), (311) and (222) crystal face, does not has oxidation peak and the Ni of Ni
Oxide peak, and compare the diffraction maximum of Pt simple substance and offset to high position, show that Ni enters in Pt lattice,
Form Pt-Ni alloy..
10, preparing non-loading type PtNi nanometer electrical catalyst, the mol ratio of Pt Yu Ni is 1:1.
(1) preparation of metal carbonyl clusters solution: weigh platiniferous for Pt:Ni=1:1 ratio in molar ratio
Compound and nickel acetate are dissolved in methyl alcohol, and stirring is to being completely dissolved；In the solution being dissolved with metal ion
Add sodium acetate and NaOH, control pH value of solution=8；CO gas it is passed through again in reaction system
Remove in system after air, obtain metal carbonyl clusters solution at 80 DEG C of reaction 20h.
(2) sacrifice template to inject: at N2Or under CO gas shield, in metal carbonyl clusters solution
Add quantitative magnesium oxide carrier, continue stirring and make magnesium oxide dispersion uniform.
(3) coreduction of metal cluster compound: be passed through air after reaction system is cooled to 20 DEG C, will configuration
Good sodium borohydride solution joins in reaction system, and sodium borohydride and Ni ion mol ratio are 10:1, continue
Filtration washing after continuous reaction 18h, then at 60 DEG C of dry 4h.
(4) catalyst is heat-treated: by dried product exhibited at H2With under the mixed atmosphere of Ar, at 500 DEG C
After condition carries out being heat-treated 2h, it is passed through N230min takes out after making product cooling.
(5) dissolving of template is sacrificed: continue after the sample after cooling adds a certain amount of sulfuric acid solution
Stirring a period of time, then it is dried after filtration washing 5 times, it is thus achieved that non-loading type PtNi nanometer electrical catalyst.
11, preparation carrying capacity is the support type PtCr/C nanometer electrical catalyst of 60%, and the mol ratio of Pt with Cr is
2:1。
(1) synthesis of metal carbonyl clusters: weigh platiniferous chemical combination for Pt:Cr=2:1 ratio in molar ratio
Thing and chromium chloride are dissolved in methyl alcohol, and stirring is to being completely dissolved；Add in the solution be dissolved with metal ion
Sodium acetate and NaOH, control pH value of solution=13；In reaction system, it is passed through CO gas again, continues
Continue and obtain metal carbonyl clusters solution at 60 DEG C of reaction 18h.
(2) injection of carrier: add quantitative carbon black in solution, making metal ladings is 60% continuation stirring
Make it be uniformly dispersed.
(3) coreduction of metal cluster compound: be passed through air after reaction system is cooled to 30 DEG C, will configuration
Good sodium borohydride solution joins in reaction system, and sodium borohydride and Cr ion mol ratio are 25:1, continue
Filtration washing after continuous reaction 24h, then at 60 DEG C of dry 4h.
(4) catalyst is heat-treated: by dried product exhibited at H2With under Ar mixed atmosphere 800 DEG C of conditions
It is passed through N after carrying out being heat-treated 20h230min, takes out after making product cooling, it is thus achieved that carrying capacity is the PtCr of 60%
Nanometer electrical catalyst, carrier is C.
12, preparing non-loading type PtCr nanometer electrical catalyst, the mol ratio of Pt Yu Cr is 1:1.
(1) synthesis of catalyst precursor metal carbonyl clusters: be Pt:Cr=1:1 ratio in molar ratio
Weighing and be dissolved in methyl alcohol containing platinum compounds and chromium chloride, stirring is to being completely dissolved；To being dissolved with metal ion
Solution in add sodium acetate and NaOH, control pH value of solution=8；An oxygen it is passed through again in reaction system
Change carbon gas and remove in system after air, obtain metal carbonyl clusters solution at 80 DEG C of reaction 20h.
(2) sacrifice template to inject: at N2Or under CO gas shield, in metal carbonyl clusters solution
Add quantitative magnesia, continue stirring and make magnesium oxide dispersion uniform.
(3) coreduction of metal cluster compound: be passed through air after reaction system is cooled to 20 DEG C, will configuration
Good sodium borohydride solution joins in reaction system, and sodium borohydride and Cr ion mol ratio are 10:1, continue
Filtration washing after continuous reaction 18h, is then dried 4h at 60 DEG C.
(4) catalyst is heat-treated: by dried product exhibited at H2With under the mixed atmosphere of Ar, at 500 DEG C
Condition is passed through N after carrying out being heat-treated 2h230min, takes out after making product cooling.
(5) dissolving of template is sacrificed: continue after the sample after cooling adds a certain amount of sulfuric acid solution
Stirring a period of time, then it is dried after filtration washing 5 times, it is thus achieved that non-loading type PtCr nanometer electrical catalyst.
13, preparation carrying capacity is the PtCu/C nanometer electrical catalyst of 60%, and the mol ratio of Pt and Cu is 2:1.
(1) preparation of metal carbonyl clusters solution: weigh platiniferous for Pt:Cu=2:1 ratio in molar ratio
Compound and copper chloride are dissolved in methyl alcohol, and stirring is to being completely dissolved；In the solution being dissolved with metal ion
Add sodium acetate and NaOH, control pH value of solution=13；CO gas it is passed through again in reaction system,
Continue to obtain metal carbonyl clusters solution at 60 DEG C of reaction 18h.
(2) injection of carrier: add quantitative carbon black in solution, making metal ladings is 60%, continues to stir
Mix and make it be uniformly dispersed.
(3) coreduction of metal cluster compound: be passed through air after reaction system is cooled to 30 DEG C, will configuration
Good sodium borohydride solution joins in reaction system, and sodium borohydride is 25:1 with the mol ratio of Cu ion,
Continue filtration washing after reaction 24h, then at 60 DEG C of dry 4h.
(4) catalyst is heat-treated: by dried product exhibited at H2With under the mixed atmosphere of Ar, at 800 DEG C
After condition carries out being heat-treated 20h, it is passed through N230min, takes out after making product cooling, it is thus achieved that carrying capacity is 60%
PtCu nanometer electrical catalyst, carrier is C.
14, preparing unsupported PtCu nanometer electrical catalyst, the mol ratio of Pt and Cu is 1:1.
(1) preparation of metal carbonyl clusters solution: weigh platiniferous for Pt:Cu=1:1 ratio in molar ratio
Compound and copper chloride are dissolved in methyl alcohol, and stirring is to being completely dissolved；In the solution being dissolved with metal ion
Add sodium acetate and NaOH, control pH value of solution=8；CO gas it is passed through again in reaction system
Remove in system after air, obtain metal carbonyl clusters solution at 80 DEG C of reaction 20h.
(2) sacrifice template to inject: at N2Or under CO gas shield, in metal carbonyl clusters solution
Add quantitative magnesia, continue stirring and make magnesium oxide dispersion uniform.
(3) coreduction of metal cluster compound: be passed through air after reaction system is cooled to 20 DEG C, will configuration
Good sodium borohydride solution joins in reaction system, and sodium borohydride and Cu ion mol ratio are 10:1, continue
Filtration washing after continuous reaction 18h, is then dried 4h at 60 DEG C.
(4) catalyst is heat-treated: by dried product exhibited at H2With under the mixed atmosphere of Ar, at 500 DEG C
Condition carries out being heat-treated 2h, then passes to N230min, takes out after making product cooling.
(5) dissolving of template is sacrificed: continue after the sample after cooling adds a certain amount of sulfuric acid solution
Stirring a period of time, then it is dried after filtration washing 5 times, it is thus achieved that non-loading type PtCu nanometer electrical catalyst.
15, preparation carrying capacity is the Pt Pd/C nanometer electrical catalyst of 60%, and the mol ratio of Pt Yu Pd is 2:1.
(1) preparation of metal carbonyl clusters solution: weigh platiniferous for Pt:Pd=2:1 ratio in molar ratio
Compound and palladium bichloride are dissolved in methyl alcohol, and stirring is to being completely dissolved；In the solution being dissolved with metal ion
Add sodium acetate and NaOH, control pH value of solution=13；CO gas it is passed through again in reaction system,
Continue to react 18h at 60 DEG C, obtain metal carbonyl clusters solution.
(2) injection of carrier: add quantitative carbon black in solution, making metal ladings is 60%, continues to stir
Mix and make it be uniformly dispersed.
(3) coreduction of metal cluster compound: be passed through air after reaction system is cooled to 30 DEG C, will configuration
Good sodium borohydride solution joins in reaction system, and sodium borohydride and Pd ion mol ratio are 25:1, continue
Filtration washing after continuous reaction 24h, is then dried 4h under the conditions of 60 DEG C.
(4) catalyst is heat-treated: by dried product exhibited at H2With under Ar mixed atmosphere, at 800 DEG C of bars
Part carries out being heat-treated 20h, then passes to N230min, takes out after making product cooling, it is thus achieved that carrying capacity is 60%
PtPd nanometer electrical catalyst, carrier is C.
16, preparing non-loading type Pt Pd nanometer electrical catalyst, the mol ratio of Pt and Pd is 1:1.
(1) preparation of metal carbonyl clusters solution: weigh platiniferous for Pt:Pd=1:1 ratio in molar ratio
Compound and palladium bichloride, be dissolved in methyl alcohol, and stirring is to being completely dissolved；To the solution being dissolved with metal ion
Middle addition sodium acetate and NaOH, control pH value of solution=8；Carbon monoxide gas it is passed through again in reaction system
Body is removed in system after air, obtains metal carbonyl clusters solution at 80 DEG C of reaction 20h.
(2) sacrifice template to inject: at N2Or under CO gas shield, in metal carbonyl clusters solution
Add quantitative magnesium oxide carrier, continue stirring and make magnesium oxide dispersion uniform.
(3) coreduction of metal cluster compound: be passed through air after reaction system is cooled to 20 DEG C, will configuration
Good sodium borohydride solution joins in reaction system, and sodium borohydride and Pd ion mol ratio are 10:1, continue
Filtration washing, then 60 DEG C of dry 4h after continuous reaction 18h.
(4) catalyst is heat-treated: by dried product exhibited at H2With under the mixed atmosphere of Ar, at 500 DEG C
After condition carries out being heat-treated 2h, it is passed through N230min, takes out after making product cooling.
(5) dissolving of template is sacrificed: continue after the sample after cooling adds a certain amount of sulfuric acid solution
Stirring a period of time, then it is dried after filtration washing 8 times, it is thus achieved that for non-loading type PtPd nano electro-catalytic
Agent.
17, preparation carrying capacity is the Pt Ag/C nanometer electrical catalyst of 60%, and the mol ratio of Pt Yu Ag is 2:1.
(1) synthesis of metal carbonyl clusters solution: weigh platiniferous for Pt:Ag=2:1 ratio in molar ratio
Compound and silver chlorate are dissolved in methyl alcohol, and stirring is to being completely dissolved；In the solution being dissolved with metal ion
Add sodium acetate and NaOH, control pH value of solution=13；CO gas it is passed through again in reaction system,
Continue to react 18h at 60 DEG C, obtain metal carbonyl clusters solution.
(2) injection of carrier: add quantitative carbon black in solution, making metal ladings is 60%, continues to stir
Mix and make it be uniformly dispersed.
(3) coreduction of metal cluster compound: be passed through air after reaction system is cooled to 30 DEG C, will configuration
Good sodium borohydride solution joins in reaction system, and sodium borohydride and Ag ion mol ratio are 25:1, continue
Filtration washing, then 60 DEG C of dry 4h after continuous reaction 24h.
(4) catalyst is heat-treated: by dried product exhibited at H2With under the mixed atmosphere of Ar, at 800 DEG C
Condition carries out being heat-treated 20h, then passes to N230min, takes out after making product cooling, it is thus achieved that carrying capacity is 60%
PtAg nanometer electrical catalyst, carrier is C.
Embodiment 18, preparing non-loading type PtAg nanometer electrical catalyst, the mol ratio of Pt Yu Ag is 1:1.
(1) preparation of metal carbonyl clusters solution: weigh platiniferous for Pt:Ag=1:1 ratio in molar ratio
Compound and silver chlorate are dissolved in methyl alcohol, and stirring is to being completely dissolved；In the solution being dissolved with metal ion
Add sodium acetate and NaOH, control pH value of solution=8；CO gas it is passed through again in reaction system
Remove in system after air, obtain metal carbonyl clusters solution at 80 DEG C of reaction 20h.
(2) sacrifice template to inject: at N2Or under CO gas shield, in metal carbonyl clusters solution
Add quantitative magnesia, continue stirring and make magnesium oxide dispersion uniform.
(3) coreduction of metal cluster compound: be passed through air after reaction system is cooled to 20 DEG C, will configuration
Good sodium borohydride solution joins in reaction system, and sodium borohydride and Ag ion mol ratio are 10:1, continue
Filtration washing after continuous reaction 18h, is then dried 4h under the conditions of 60 DEG C.
(4) catalyst is heat-treated: by dried product exhibited at H2With under the mixed atmosphere of Ar, at 500 DEG C
Condition carries out being heat-treated 2h, then passes to N230min, takes out after making product cooling.
(5) dissolving of template is sacrificed: continue after the sample after cooling adds a certain amount of sulfuric acid solution
Stirring a period of time, then it is dried after filtration washing 5 times, it is thus achieved that non-loading type PtAg nanometer electrical catalyst.
The above is only the preferred embodiment of the present invention, it is noted that common for the art
Technical staff, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these
Improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. the preparation method of a nanometer electrical catalyst, it is characterised in that including:
Thering is provided metal carbonyl clusters solution, described metal carbonyl clusters comprises platinum and the first metal；
The carrying capacity of platinum and the first metal in described metal carbonyl clusters is adjusted to 20%～100%；
In described metal carbonyl clusters solution, it is passed through oxidizing gas, and adds reducing agent, react；
Reacted product is dried；
Dried product exhibited is heat-treated.
The preparation method of nanometer electrical catalyst the most according to claim 1, it is characterised in that described in carry out
During reaction, the temperature of metal carbonyl clusters solution is 20 DEG C～100 DEG C, reducing agent and the first metal
Mol ratio is 5～25:1.
The preparation method of nanometer electrical catalyst the most according to claim 1, it is characterised in that described first
Metal is the one in Fe, Co, Ni, Cr, Cu, Ru, Pd and Ag.
The preparation method of nanometer electrical catalyst the most according to claim 1, it is characterised in that prepare metal
The method of Carbonyl Clusters solution includes:
Platinum compounds will be contained and dissolve formation solution containing the first metallic compound；
In described solution, add sodium acetate and NaOH, be 7～13 to regulate the pH value of described solution；
Being passed through carbon monoxide in described solution, keeping solution temperature is 20 DEG C～80 DEG C, maintains 2 hours～24
Hour.
The preparation method of nanometer electrical catalyst the most according to claim 1, it is characterised in that to described gold
Belong to Carbonyl Clusters solution adding carrier or sacrificing template and adjust platinum in described metal carbonyl clusters
Carrying capacity with the first metal.
The preparation method of nanometer electrical catalyst the most according to claim 5, it is characterised in that described carrier
Material include at least one in carbon black, Graphene, CNT and mesoporous carbon；Described sacrifice
Mould material includes at least one in nano magnesia, nano aluminium oxide and nano zine oxide.
The preparation method of nanometer electrical catalyst the most according to claim 6, it is characterised in that also include:
Product after heat treated adds acid solution, to remove described sacrifice template.
The preparation method of nanometer electrical catalyst the most according to claim 7, it is characterised in that described acid is molten
Liquid is the one in sulfuric acid, hydrochloric acid, nitric acid and perchloric acid.
The preparation method of nanometer electrical catalyst the most according to claim 1, it is characterised in that described reduction
Agent includes: the one in sodium borohydride, hydrazine hydrate and ascorbic acid.
The preparation method of nanometer electrical catalyst the most according to claim 1, it is characterised in that at described heat
The temperature of reason is 100 DEG C～800 DEG C, and the time is 2 hours～20 hours.
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