CN109055961A - A kind of noble metal support type nanometer frame catalyst and its preparation method and application - Google Patents
A kind of noble metal support type nanometer frame catalyst and its preparation method and application Download PDFInfo
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- CN109055961A CN109055961A CN201810994389.4A CN201810994389A CN109055961A CN 109055961 A CN109055961 A CN 109055961A CN 201810994389 A CN201810994389 A CN 201810994389A CN 109055961 A CN109055961 A CN 109055961A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/097—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds comprising two or more noble metals or noble metal alloys
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention provides a kind of noble metal support type nanometer frame catalyst and its preparation method and application, and the catalyst includes noble metal and transition metal hydroxide；The catalyst is in hollow Nano mount structure.Catalyst of the present invention is in hollow Nano mount structure, and activation specific surface area is larger, and wall thickness is smaller, and mass transfer is apart from short；The catalyst optimizes electronic structure between the two with noble-metal-supported nickel cobalt hydroxide, and catalyst stability is strong, can effectively reduce the overpotential of catalytic hydrogen evolution reaction, and current density is 10mA cm‑2When, overpotential is only 60mV；Method for preparing catalyst of the present invention is simple, with short production cycle, has a extensive future.
Description
Technical field
The invention belongs to catalyst technical field, it is related to a kind of noble metal support type nanometer frame catalyst and preparation method thereof
And purposes more particularly to a kind of noble-metal-supported nickel cobalt hydroxide nano frame catalyst and its preparation method and application.
Background technique
With the gradual depletion of fossil energy, the development and utilization of renewable energy is paid more and more attention, and wherein hydrogen is made
The problem of CO2 emission is not present for a kind of renewable and clean energy resource, when as the energy, meanwhile, hydrogen has higher
Energy density, be a kind of ideal energy that can replace fossil energy.Electrolysis water is that prepare hydrogen be a kind of common hydrogen manufacturing side
Method, available high-purity hydrogen under the action of catalyst, therefore efficiently the preparation of evolving hydrogen reaction catalyst is that the current energy is asked
One of research emphasis of topic.
Since electrolysis water liberation of hydrogen belongs to electrocatalytic reaction, liberation of hydrogen catalyst is generally as electrode material or is coated in electricity
It is extremely upper to use.Currently, the research of elctro-catalyst is concentrated mainly on the following aspects: reducing the dosage of noble metal, regulation catalysis
The electronic structure of agent, prepares composite catalyst；The space structure and pattern of regulation catalyst, raising specific surface area of catalyst,
Stability；The purpose of the above corrective measure is to prepare the catalyst of high activity, high stability, low cost.
108003355 A of CN discloses a kind of synthetic method of hollow cube PtCu nanometers of frame materials, by using one
Pot coreduction solvent-thermal method, by metal precursor acetylacetone,2,4-pentanedione platinum and copper chloride, then is aided with regulatory molecule cetyl trimethyl
Ammonium chloride, reducing agent ethanol amine and solvent oleyl amine, PtCu nanometers of frame materials are prepared in solvothermal, but this method is to anti-
Answer the requirement of condition more stringent, the formation of hollow cube is more difficult.105990588 A of CN discloses a kind of difunctional
Pd/Ni-Mo/C composite catalyst and preparation method thereof, the catalyst load NiMo alloy, so using conductive carbon as carrier on it
Precious metals pd part cladding is formed thereon afterwards, is first supported on a certain proportion of NiMo by dipping-high temperature reduction method
Carbon support obtains NiMo/C, is then selectively partially coated on NiMo/C by ethylene glycol circumfluence method a certain proportion of
Precious metals pd improves metal surface electronic structure by the interaction of noble metal and transition metal, so that it is living to improve hydrogen reduction
Property, but the catalyst preparation process step is more, while being related to high temperature, easily cause pattern to change, stability still needs to mention
It is high.
In conclusion there is still a need for seek method easy to operate, that cost of material is low, and institute for the preparation of Electrocatalytic Activity for Hydrogen Evolution Reaction agent
Obtain catalyst catalytic activity with higher and stability.
Summary of the invention
In view of the problems of the existing technology, the purpose of the present invention is to provide a kind of catalysis of noble metal support type nanometer frame
Agent and its preparation method and application, by the electronics knot that noble-metal-supported on transition metal hydroxide, is regulated and controled to catalyst
Structure, stability is strong, and the catalyst is in hollow Nano mount structure, and specific surface area is larger, and active site is more；The above characteristic to urge
Agent is used to have lower overpotential when evolving hydrogen reaction, can effectively enhance catalytic activity.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of noble metal support type nanometer frame catalyst, your gold the catalyst includes
Category and transition metal hydroxide；The catalyst is in hollow Nano mount structure.
In the present invention, the catalyst is formed on transition metal hydroxide by noble-metal-supported, by noble metal with
Synergistic effect between transition metal hydroxide, between different transition metal, enables its original electronic structure to regulate and control, and drops
It is low for catalytic hydrogen evolution when overpotential, improve its electrocatalysis characteristic；The catalyst be in hollow Nano mount structure, have compared with
Big electro-active surface product, shortens the transmission range of substance, improves catalytic efficiency.
It is used as currently preferred technical solution below, but not as the limitation of technical solution provided by the invention, passes through
Following technical scheme can preferably reach and realize technical purpose and beneficial effect of the invention.
As currently preferred technical solution, the noble metal includes any one in palladium, ruthenium, platinum or gold or at least two
The combination of kind, the combination is typical but non-limiting example has: the combination of the combination of palladium and ruthenium, ruthenium and platinum, the combination of platinum and gold,
Palladium, ruthenium and combination of gold etc., preferably palladium.
Preferably, the transition metal hydroxide includes nickel cobalt hydroxide.
Preferably, the partial size of the catalyst is 400~500nm, such as 400nm, 420nm, 440nm, 460nm, 480nm
Or 500nm etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, the wall thickness of the catalyst be 8~20nm, such as 8nm, 10nm, 12nm, 14nm, 16nm, 18nm or
20nm etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
In the present invention, structure, size and the wall thickness of the catalyst in addition to being determined by template used dose of relevant parameter,
Also related with the mass ratio of reaction reagent used, the selection of each parameter is to be conducive to improve the catalytic activity and stabilization of catalyst
Property carrys out comprehensive regulation.
Preferably, the specific surface area of the catalyst is 40~60m2/ g, such as 40m2/g、42m2/g、45m2/g、48m2/
g、50m2/g、54m2/g、57m2/ g or 60m2/ g etc., it is not limited to cited numerical value, interior other of the numberical range are not arranged
The numerical value of act is equally applicable.
As currently preferred technical solution, the mass fraction of noble metal is 5~30wt% in the catalyst, such as
5wt%, 10wt%, 15wt%, 20wt%, 25wt% or 30wt% etc., it is not limited to cited numerical value, the numerical value model
Other unlisted numerical value are equally applicable in enclosing.
Preferably, the mass ratio of nickel and cobalt is (0.2~5) in the catalyst: 1, such as 0.2:1,0.25:1,0.33:
1,0.5:1,1:1,2:1,3:1,4:1 or 5:1 etc., it is not limited to cited numerical value, interior other of the numberical range are not arranged
The numerical value of act is equally applicable.
Second aspect, it is described the present invention provides a kind of preparation method of above-mentioned noble metal support type nanometer frame catalyst
Method the following steps are included:
(1) cuprous nano frame dispersion liquid is mixed with nickel salt and cobalt salt, obtains mixed liquor；
(2) thiosulfate solution is added in the mixed liquor obtained to step (1), reacts, obtains nickel cobalt hydroxide
Object；
(3) reducing agent is added after mixing the nickel cobalt hydroxide solution that step (2) obtains with precious metal salt, occurs anti-
It answers, obtains noble metal support type nanometer frame catalyst.
As currently preferred technical solution, the partial size of step (1) the cuprous nano frame is 400~500nm,
Such as 400nm, 420nm, 440nm, 460nm, 480nm or 500nm etc., it is not limited to cited numerical value, the numerical value model
Other unlisted numerical value are equally applicable in enclosing.
Preferably, the cuprous nano frame is in octahedra hollow structure.
Preferably, the wall thickness of step (1) the cuprous nano frame be 8~20nm, such as 8nm, 10nm, 12nm,
14nm, 16nm, 18nm or 20nm etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range
It is equally applicable.
Preferably, the cuprous nano frame preparation method the following steps are included:
(a) mixed liquor including mantoquita, sodium potassium tartrate tetrahydrate and alkali is prepared；
(b) palladium chloride and glucose are added into the mixed liquor that step (a) obtains, reacts, obtains cuprous oxide and receive
Rice frame.
In the present invention, when preparing cuprous nano frame, alkaline cupric tartrate test solution is configured first, by by mantoquita, wine
It is formed after stone acid potassium sodium and alkali soluble solution, palladium chloride and glucose is then added, glucose is as reducing agent, and palladium chloride is as catalysis
Cupric tartrate complex is reduced to cuprous oxide by agent, and the micro amount of oxygen in solution slowly will oxidation under the action of palladium later
It is cuprous to be oxidized to bivalent cupric ion, and realize the selective etch of cuprous oxide, obtain cuprous nano frame.
As currently preferred technical solution, step (a) mantoquita includes appointing in copper sulphate, copper acetate or copper nitrate
It anticipates a kind of or at least two combinations, the combination typical case but non-limiting example has: the combination of copper sulphate and copper acetate, acetic acid
The combination of copper and copper nitrate, copper sulphate, copper acetate and combination of copper nitrate etc..
Preferably, step (a) alkali includes potassium hydroxide and/or sodium hydroxide.
Preferably, the mass ratio of step (a) mantoquita and step (b) palladium chloride is (20~70): 1, such as 20:
1,30:1,40:1,50:1,60:1 or 70:1 etc., it is not limited to cited numerical value, other are unlisted in the numberical range
Numerical value it is equally applicable.
Preferably, the mass ratio of step (a) mantoquita and step (b) glucose is (0.6~0.9): 1, such as
0.6:1,0.65:1,0.7:1,0.75:1,0.8:1,0.85:1 or 0.9:1 etc., it is not limited to cited numerical value, the number
It is equally applicable to be worth other unlisted numerical value in range.
Preferably, step (b) reaction carries out under water bath condition.
Preferably, the bath temperature is 60~90 DEG C, such as 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C or 90 DEG C
Deng it is not limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, the water bath time be 2~4h, such as 2h, 2.25h, 2.5h, 2.75h, 3h, 3.25h, 3.5h,
3.75h or 4h etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
As currently preferred technical solution, the solvent of step (1) the cuprous oxide dispersion liquid includes water and ethyl alcohol.
Preferably, the volume ratio of the water and ethyl alcohol be (0.5~2): 1, for example, 0.5:1,0.8:1,1:1,1.2:1,
1.5:1,1.8:1 or 2:1 etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same
It is applicable in.
Preferably, the mass ratio of step (1) the cuprous nano frame and nickel salt and cobalt salt is (0.8~1.2): 1, example
Such as 0.8:1,0.85:1,0.9:1,0.95:1,1.0:1,1.05:1,1.1:1,1.15:1 or 1.2:1, it is not limited to institute
The numerical value enumerated, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, step (1) described nickel salt includes any one in nickel nitrate, nickel chloride or nickel sulfate or at least two
Combination, the combination is typical but non-limiting example has: the combination of the combination of nickel nitrate and nickel chloride, nickel chloride and nickel sulfate,
Nickel nitrate, nickel chloride and combination of nickel sulfate etc..
Preferably, step (1) described cobalt salt includes any one in cobalt nitrate, cobalt chloride or cobaltous sulfate or at least two
Combination, the combination is typical but non-limiting example has: the combination of the combination of cobalt nitrate and cobalt chloride, cobalt chloride and cobaltous sulfate,
Cobalt nitrate, cobalt chloride and combination of cobaltous sulfate etc..
Preferably, the mass ratio of step (1) nickel salt and cobalt salt is (0.2~5): 1, such as 0.2:1,0.25:1,
0.33:1,0.5:1,1:1,2:1,3:1,4:1 or 5:1 etc., it is not limited to cited numerical value, in the numberical range other
Unlisted numerical value is equally applicable.
Preferably, step (1) described mixed liquor further includes surfactant.
Preferably, the surfactant includes polyvinylpyrrolidone and/or lauryl sodium sulfate.
Preferably, the mass ratio of the surfactant and step (1) described cuprous nano frame is (30~35): 1,
Such as 30:1,31:1,32:1,33:1,34:1 or 35:1 etc., it is not limited to cited numerical value, in the numberical range its
His unlisted numerical value is equally applicable.
In the present invention, nickel ion and cobalt ions can be strapped near cuprous oxide surface by the use of surfactant,
Be conducive to still maintain a nanometer mount structure after nickel cobalt hydroxide is formed, while also can control reaction rate, avoids cuprous oxide
Cross fast response.
Preferably, step (1) described mixed liquor obtains stir process.
As currently preferred technical solution, the concentration of step (2) described thiosulfate solution is 0.5~
1.5mol/L, such as 0.5mol/L, 0.6mol/L, 0.8mol/L, 1.0mol/L, 1.2mol/L, 1.4mol/L or 1.5mol/L
Deng it is not limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, the adding manner of step (2) described thiosulfate solution is to be added dropwise.
Preferably, the molar ratio of step (2) thiosulfate and step (1) described cuprous nano frame is (70
~74): 1, such as 70:1,70.5:1,71:1,71.5:1,72:1,72.5:1,73:1,73.5:1 or 74:1 etc., but simultaneously not only
It is limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
In the present invention, with cuprous oxide complexation reaction can occur for thiosulfate, raw while cuprous oxide is dissolved
At the nickel ion and cobalt ions generation hydroxide precipitating in hydroxide ion, with solution, it is covered on former cuprous nano frame
Surface, ultimately generate nickel cobalt hydroxide nano frame.
In addition, mode of the thiosulfate solution preferably with dropwise addition, can avoid because thiosulfate is locally excessive and anti-
It answers too fast, has little time to generate hydroxide precipitating, product can not form a nanometer mount structure.
Preferably, step (2) described thiosulfate includes appointing in sodium thiosulfate, potassium thiosulfate or ATS (Ammonium thiosulphate)
It anticipates a kind of or at least two combinations, the combination is typical but non-limiting example has: sodium thiosulfate and potassium thiosulfate
Combination, the combination of potassium thiosulfate and ATS (Ammonium thiosulphate), sodium thiosulfate, potassium thiosulfate and combination of ATS (Ammonium thiosulphate) etc..
Preferably, step (2) reaction carries out under agitation.
Preferably, step (2) reaction temperature is 20~40 DEG C, such as 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C or 40 DEG C etc.,
It is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, step (2) reaction time be 10~20min, such as 10min, 12min, 14min, 16min,
18min or 20min etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, step (2) is described after reaction, through filtering, carrying out washing treatment, obtains nickel cobalt hydroxide nano frame.
As currently preferred technical solution, step (3) described precious metal salt includes palladium salt, ruthenium salt, platinum salt or gold salt
In any one or at least two combination, the combination is typical but non-limiting example has: the combination of palladium salt and ruthenium salt, palladium salt
With the combination of platinum salt, the combination of platinum salt and gold salt, palladium salt, ruthenium salt and combination of platinum salt etc., preferably palladium salt.
Preferably, the palladium salt includes the group of any one in chlorine palladium acid sodium, potassium chloropalladate or chlorine palladium acid or at least two
It closes, the combination is typical but non-limiting example has: the combination of chlorine palladium acid sodium and potassium chloropalladate, the group of potassium chloropalladate and chlorine palladium acid
It closes, chlorine palladium acid sodium, potassium chloropalladate and combination of chlorine palladium acid etc..
Preferably, the mass ratio of step (3) precious metal salt and nickel cobalt hydroxide is (15~50): 1, such as 15:
1,20:1,25:1,30:1,35:1,40:1,45:1 or 50:1 etc., it is not limited to cited numerical value, in the numberical range
Other unlisted numerical value are equally applicable.
Preferably, step (3) described reducing agent includes sodium borohydride.
Preferably, the mass ratio of step (3) precious metal salt and reducing agent is (0.065~0.125): 1, such as
0.065:1,0.07:1,0.08:1,0.09:1,0.1:1,0.11:1 or 0.125:1 etc., it is not limited to cited number
Value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, step (3) reaction carries out under agitation.
Preferably, step (3) reaction temperature is 20~40 DEG C, such as 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C or 40 DEG C etc.,
It is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, step (3) reaction time be 5~15min, such as 5min, 6min, 8min, 10min, 12min,
14min or 15min etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, step (3) is described after reaction, is washed, is dried to reaction product, obtains noble metal support type
Nanometer frame catalyst.
The third aspect, the present invention provides a kind of purposes of above-mentioned noble metal support type nanometer frame catalyst, the catalysis
Agent is used as evolving hydrogen reaction catalyst.
Compared with prior art, the invention has the following advantages:
(1) catalyst of the present invention is optimized electronic structure between the two, is urged with noble-metal-supported nickel cobalt hydroxide
Agent stability is strong, can effectively reduce the overpotential of catalytic hydrogen evolution reaction；
(2) catalyst of the present invention is in hollow Nano mount structure, and large specific surface area, electro-active site is more, and wall thickness is smaller,
Mass transfer can accelerate reaction and carry out apart from short；
(3) method for preparing catalyst of the present invention is simple, with short production cycle, and the current density of catalytic hydrogen evolution reaction is
10mA cm-2When, overpotential is only 60mV.
Detailed description of the invention
Fig. 1 is the SEM figure for the palladium load nanometer frame catalyst that the embodiment of the present invention 4 provides；
Fig. 2 is the palladium load nanometer frame catalyst that the embodiment of the present invention 4 provides and the nanometer frame catalyst that comparative example 1 provides
Linear Circulation volt-ampere polarization curve.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only simple example of the invention, does not represent or limit the scope of the present invention, this
Invention protection scope is subject to claims.
Specific embodiment of the invention part provides a kind of noble metal support type nanometer frame catalyst and preparation method thereof,
The catalyst includes noble metal and transition metal hydroxide；The catalyst is in hollow Nano mount structure.
Preparation method includes the following steps:
(1) cuprous nano frame dispersion liquid is mixed with nickel salt and cobalt salt, obtains mixed liquor；
(2) thiosulfate solution is added in the mixed liquor obtained to step (1), reacts, obtains nickel cobalt hydroxide
Object；
(3) reducing agent is added after mixing the nickel cobalt hydroxide solution that step (2) obtains with precious metal salt, occurs anti-
It answers, obtains noble metal support type nanometer frame catalyst.
The following are typical but non-limiting embodiments of the invention:
Embodiment 1:
The preparation method for present embodiments providing a kind of cuprous nano frame, the described method comprises the following steps:
(1) 0.35g copper sulphate, 1.25g sodium potassium tartrate tetrahydrate and 0.225g potassium hydroxide are separately added into water, are mixed
Liquid；
(2) 9.6mg palladium chloride and 0.450g glucose are added into the mixed liquor that step (a) obtains, stirs evenly, 75
Water-bath 3h under the conditions of DEG C obtains cuprous nano frame after centrifuge washing is dry.
Embodiment 2:
The preparation method for present embodiments providing a kind of cuprous nano frame, the described method comprises the following steps:
(1) 0.41g copper nitrate, 1.25g sodium potassium tartrate tetrahydrate and 0.161g sodium hydroxide are separately added into water, are mixed
Liquid；
(2) 20.5mg palladium chloride and 0.683g glucose are added into the mixed liquor that step (a) obtains, stirs evenly,
Water-bath 4h under the conditions of 60 DEG C obtains cuprous nano frame after centrifuge washing is dry.
Embodiment 3:
The preparation method for present embodiments providing a kind of cuprous nano frame, the described method comprises the following steps:
(1) 0.40g copper acetate, 1.25g sodium potassium tartrate tetrahydrate and 0.225g potassium hydroxide are separately added into water, are mixed
Liquid；
(2) 5.7mg palladium chloride and 0.444g glucose are added into the mixed liquor that step (a) obtains, stirs evenly, 90
Water-bath 2h under the conditions of DEG C obtains cuprous nano frame after centrifuge washing is dry.
Embodiment 4:
A kind of palladium load nanometer frame catalyst and preparation method thereof is present embodiments provided, the catalyst includes noble metal
Palladium and nickel cobalt hydroxide, wherein the mass fraction of palladium is 15wt% in the catalyst, and the mass ratio of nickel and cobalt is 1:2；
The catalyst is in hollow Nano mount structure, partial size 450nm, wall thickness 12nm.
The preparation method of the catalyst the following steps are included:
(1) water and alcohol mixeding liquid that volume ratio is 1:1 are dispersed by the cuprous nano frame 10mg that embodiment 1 obtains
In, 0.34g polyvinylpyrrolidone is then added and adds 3.3mg nickel chloride and 6.7mg cobalt chloride after mixing evenly, obtains
Mixed liquor；
(2) hypo solution of 5mL 1mol/L is added dropwise in the mixed liquor obtained to step (1), in 30 DEG C of items
It is stirred to react 15min under part, through filtering, carrying out washing treatment, obtains nickel cobalt hydroxide nano frame；
(3) the chlorine palladium acid sodium that 0.5mL 1.6mmol/L is added after the nickel cobalt hydroxide dissolution obtained step (2) is molten
Liquid adds the sodium borohydride of 1mL 0.1mol/L, and 10min is stirred to react under the conditions of 30 DEG C and obtains palladium after washing, drying
Load nanometer frame catalyst.
The palladium being prepared load nanometer frame catalyst is scanned electron microscope (SEM) characterization, SEM figure is as schemed
Shown in 1；It disperses palladium load nanometer frame catalyst in dehydrated alcohol with the concentration of 4mg/mL, 14 μ L drops is taken to handle well
Glass-carbon electrode, 10 μ L 0.1%nafion solution are added dropwise after drying again, after drying, using it as working electrode, platinum plate electrode is
To electrode, Ag/AgCl is reference electrode, using the potassium hydroxide solution of 1mol/L as electrolyte, is tested with the scanning speed of 5mV/s
Its catalytic performance to evolving hydrogen reaction, Linear Circulation volt-ampere polarization curve are as shown in Figure 2.
In the present embodiment, as shown in Figure 1, the catalyst is in hollow Nano mount structure, and partial size is about 450nm, and wall thickness is about
For 12nm；As shown in Figure 2, the catalyst is used for evolving hydrogen reaction, and current density is 10mA cm-2When, it can be obtained according to its potential value
The overpotential of the catalyst is only 60mV out.
Embodiment 5:
A kind of palladium load nanometer frame catalyst and preparation method thereof is present embodiments provided, the catalyst includes noble metal
Palladium and nickel cobalt hydroxide, wherein the mass fraction of palladium is 5wt% in the catalyst, and the mass ratio of nickel and cobalt is 1:5；
The catalyst is in hollow Nano mount structure, partial size 400nm, wall thickness 10nm.
The preparation method of the catalyst the following steps are included:
(1) water and ethyl alcohol mixing that volume ratio is 0.5:1 are dispersed by the cuprous nano frame 10mg that embodiment 2 obtains
In liquid, 0.30g lauryl sodium sulfate is then added and adds 1.4mg nickel nitrate and 7.0mg cobalt nitrate after mixing evenly, obtains
To mixed liquor；
(2) the thiosulfuric acid potassium solution of 3.25mL 1.5mol/L is added dropwise in the mixed liquor obtained to step (1),
It is stirred to react 20min under the conditions of 20 DEG C, through filtering, carrying out washing treatment, obtains nickel cobalt hydroxide nano frame；
(3) potassium chloropalladate that 0.72mL 1.0mmol/L is added after the nickel cobalt hydroxide dissolution obtained step (2) is molten
Liquid adds the sodium borohydride of 1.4mL 0.05mol/L, and 5min is stirred to react under the conditions of 40 DEG C and is obtained after washing, drying
Palladium loads nanometer frame catalyst.
The palladium being prepared load nanometer frame catalyst is used for catalytic hydrogen evolution reaction, tests its catalytic performance, the survey
Strip part is referring to embodiment 4.
In the present embodiment, the catalyst is used for evolving hydrogen reaction, and current density is 10mA cm-2When, overpotential is only
75mV。
Embodiment 6:
A kind of palladium load nanometer frame catalyst and preparation method thereof is present embodiments provided, the catalyst includes noble metal
Palladium and nickel cobalt hydroxide, wherein the mass fraction of palladium is 30wt% in the catalyst, and the mass ratio of nickel and cobalt is 5:1；
The catalyst is in hollow Nano mount structure, partial size 500nm, wall thickness 20nm.
The preparation method of the catalyst the following steps are included:
(1) water and alcohol mixeding liquid that volume ratio is 2:1 are dispersed by the cuprous nano frame 10mg that embodiment 3 obtains
In, 0.35g polyvinylpyrrolidone is then added and adds 9.7mg nickel chloride and 2.3mg cobaltous sulfate after mixing evenly, obtains
Mixed liquor；
(2) the thiosulfuric acid ammonium salt solution of 10.25mL 0.5mol/L is added dropwise in the mixed liquor obtained to step (1),
It is stirred to react 10min under the conditions of 40 DEG C, through filtering, carrying out washing treatment, obtains nickel cobalt hydroxide nano frame；
(3) the chlorine palladium acid solution of 1.1mL 2.0mmol/L is added after the nickel cobalt hydroxide dissolution obtained step (2),
The sodium borohydride for adding 0.85mL 0.2mol/L is stirred to react 15min at 20 °C and obtains palladium after washing, drying
Load nanometer frame catalyst.
The palladium being prepared load nanometer frame catalyst is used for catalytic hydrogen evolution reaction, tests its catalytic performance, the survey
Strip part is referring to embodiment 4.
In the present embodiment, the catalyst is used for evolving hydrogen reaction, and current density is 10mA cm-2When, overpotential is only
68mV。
Embodiment 7:
A kind of platinum load nanometer frame catalyst and preparation method thereof is present embodiments provided, the catalyst includes noble metal
Platinum and nickel cobalt hydroxide, wherein the mass fraction of platinum is 10wt% in the catalyst, and the mass ratio of nickel and cobalt is 1:1；
The catalyst is in hollow Nano mount structure, partial size 450nm, wall thickness 15nm.
The preparation method of the catalyst is only that referring to the method in embodiment 4, difference: being added in step (3)
The platinic sodium chloride solution 0.2mL of 1.6mmol/L obtains platinum load nanometer frame catalyst.
The platinum being prepared load nanometer frame catalyst is used for catalytic hydrogen evolution reaction, tests its catalytic performance, the survey
Strip part is referring to embodiment 4.
In the present embodiment, the catalyst is used for evolving hydrogen reaction, and current density is 10mA cm-2When, overpotential is only
70mV。
Embodiment 8:
A kind of palladium ruthenium load nanometer frame catalyst and preparation method thereof is present embodiments provided, your gold the catalyst includes
Belong to palladium, ruthenium and nickel cobalt hydroxide, wherein the mass fraction of palladium and ruthenium is 24wt%, the quality of nickel and cobalt in the catalyst
Than for 2.5:1；
The catalyst is in hollow Nano mount structure, partial size 480nm, wall thickness 18nm.
The preparation method of the catalyst is only that referring to the method in embodiment 4, difference: being added in step (3)
The ruthenium hydrochloride sodium solution 0.25mL of chlorine palladium the acid sodium solution 0.5mL and 1.6mmol/L of 1.6mmol/L obtain palladium ruthenium load nanometer
Frame catalyst.
The palladium ruthenium being prepared load nanometer frame catalyst is used for catalytic hydrogen evolution reaction, tests its catalytic performance, it is described
Test condition is referring to embodiment 4.
In the present embodiment, the catalyst is used for evolving hydrogen reaction, and current density is 10mA cm-2When, overpotential is only
65mV。
Embodiment 9:
A kind of preparation method of palladium load nanometer frame catalyst is present embodiments provided, the method is referring in embodiment 4
Method, difference is only that: step is added without polyvinylpyrrolidone in (1).
The palladium being prepared load nanometer frame catalyst is used for catalytic hydrogen evolution reaction, tests its catalytic performance, the survey
Strip part is referring to embodiment 4.
In the present embodiment, due to not having addition surfactant, the rate of complexation reaction is very fast, to transition metal ions
Bound poor, hydroxide is not easy to be deposited in cuprous oxide surface completely, causes catalyst to be not easy to maintain original structure, surely
Qualitative variation is reacted for catalytic hydrogen evolution, and current density is 10mA cm-2When, overpotential reaches 112mV.
Embodiment 10:
A kind of preparation method of palladium load nanometer frame catalyst is present embodiments provided, the method is referring in embodiment 4
Method, difference is only that: hypo solution is added at one time in step (2).
The palladium being prepared load nanometer frame catalyst is used for catalytic hydrogen evolution reaction, tests its catalytic performance, the survey
Strip part is referring to embodiment 4.
In the present embodiment, hypo solution is added at one time, and the non-uniform problem of dispersion can be brought, because of local excess
And the cuprous oxide of the part is made to react too fast, hydroxide precipitating is difficult to form a nanometer mount structure, and other parts are reacted
Degree is low, so that the production quantity of final nanometer frame catalyst is reduced, reacts for catalytic hydrogen evolution, and current density is 10mA cm-2
When, overpotential reaches 125mV.
Comparative example 1:
This comparative example provides a kind of nanometer of frame catalyst and preparation method thereof, and the catalyst includes nickel cobalt hydroxide
Object, wherein the mass ratio of nickel and cobalt is 1:2 in the catalyst；
The catalyst is in hollow Nano mount structure, partial size 440nm, wall thickness 10nm.
The preparation method of the catalyst is only that referring to the method in embodiment 4, difference: not including step (3).
The nanometer frame catalyst being prepared is used for catalytic hydrogen evolution reaction, its catalytic activity is tested, as shown in Fig. 2, institute
Test condition is stated referring to embodiment 4.
In this comparative example, the catalyst does not carry out noble-metal-supported, lacks main active component, and catalytic performance is significant
It reduces, as shown in Figure 2, the catalyst is reacted for catalytic hydrogen evolution, current density 10mAcm-2When, it can according to its potential value
Show that the overpotential of the catalyst is up to 481mV.
Comparative example 2:
This comparative example provides a kind of palladium load nanometer frame catalyst and preparation method thereof, and the catalyst includes noble metal
Palladium and nickel hydroxide, wherein the mass fraction of palladium is 15wt% in the catalyst；
The catalyst is in hollow Nano mount structure, partial size 450nm, wall thickness 12nm.
The preparation method of the catalyst is only that referring to the method in embodiment 4, difference: step is added without chlorine in (1)
Change cobalt.
The palladium being prepared load nanometer frame catalyst is used for catalytic hydrogen evolution reaction, tests its catalytic activity, the survey
Strip part is referring to embodiment 4.
In this comparative example, since cobalt chloride not being added, palladium load hydrogen nickel oxide catalyst is had to, compared with Example 4,
Lack the synergistic effect between transition metal hydroxide, catalytic activity accordingly reduces, and the current density of catalytic hydrogen evolution reaction is
10mA cm-2When, overpotential reaches 165mV.
Comparative example 3:
This comparative example provides a kind of palladium load nanometer frame catalyst and preparation method thereof, and the catalyst includes noble metal
Palladium and cobalt hydroxide, wherein the mass fraction of palladium is 15wt% in the catalyst；
The catalyst is in hollow Nano mount structure, partial size 450nm, wall thickness 12nm.
The preparation method of the catalyst is only that referring to the method in embodiment 4, difference: step is added without chlorine in (1)
Change nickel.
The palladium being prepared load nanometer frame catalyst is used for catalytic hydrogen evolution reaction, tests its catalytic activity, the survey
Strip part is referring to embodiment 4.
In this comparative example, since nickel chloride not being added, palladium load hydrogen cobalt oxide catalyst is had to, compared with Example 4,
Lack the synergistic effect between transition metal hydroxide, catalytic activity accordingly reduces, and the current density of catalytic hydrogen evolution reaction is
10mA cm-2When, overpotential reaches 135mV.
It can be seen that catalyst of the present invention with comparative example based on the above embodiments to be prepared by template of cuprous oxide
To the nickel cobalt hydroxide nano frame catalyst of noble-metal-supported, preparation method is simple, with short production cycle, has both optimized between the two
Electronic structure enhances its stability；Meanwhile the hollow Nano mount structure of the catalyst keeps its activation specific surface area larger, wall
Thick smaller, for mass transfer apart from short, reaction rate is very fast；The overpotential of the catalyst evolving hydrogen reaction significantly reduces, electricity
Current density is 10mA cm-2When, overpotential is only 60mV.
Applicant's statement, the present invention illustrate detailed preparation method and purposes of the invention, but this hair by examples detailed above
It is bright to be not limited to above-mentioned method detailed and purposes, that is, do not mean that the invention must rely on the above detailed methods to implement.
The technical personnel in the technical field are it will be clearly understood that any improvement in the present invention, equivalent transformation to raw material of the present invention and auxiliary
Addition, actual conditions and the selection of mode etc. of component are helped, all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of noble metal support type nanometer frame catalyst, which is characterized in that the catalyst includes noble metal and transition metal
Hydroxide；The catalyst is in hollow Nano mount structure.
2. catalyst according to claim 1, which is characterized in that the noble metal includes any one in palladium, ruthenium, platinum or gold
Kind or at least two combination, preferably palladium；
Preferably, the transition metal hydroxide includes nickel cobalt hydroxide；
Preferably, the partial size of the catalyst is 400~500nm；
Preferably, the wall thickness of the catalyst is 8~20nm；
Preferably, the specific surface area of the catalyst is 40~60m2/g。
3. catalyst according to claim 1 or 2, which is characterized in that the mass fraction of noble metal is 5 in the catalyst
~30wt%；
Preferably, the mass ratio of nickel and cobalt is (0.2~5) in the catalyst: 1.
4. a kind of preparation method of the catalyst as described in claim any one of 1-3, which is characterized in that the method includes following
Step:
(1) cuprous nano frame dispersion liquid is mixed with nickel salt and cobalt salt, obtains mixed liquor；
(2) thiosulfate solution is added in the mixed liquor obtained to step (1), reacts, obtains nickel cobalt hydroxide；
(3) reducing agent is added after mixing the nickel cobalt hydroxide solution that step (2) obtains with precious metal salt, reacts, obtains
To noble metal support type nanometer frame catalyst.
5. the preparation method according to claim 4, which is characterized in that the partial size of step (1) the cuprous nano frame
For 400~500nm；
Preferably, the cuprous nano frame is in octahedra hollow structure；
Preferably, the wall thickness of step (1) the cuprous nano frame is 8~20nm；
Preferably, the cuprous nano frame preparation method the following steps are included:
(a) mixed liquor including mantoquita, sodium potassium tartrate tetrahydrate and alkali is prepared；
(b) palladium chloride and glucose are added into the mixed liquor that step (a) obtains, reacts, obtains cuprous nano frame.
6. preparation method according to claim 5, which is characterized in that step (a) mantoquita includes copper sulphate, copper acetate
Any one in copper nitrate or at least two combination；
Preferably, step (a) alkali includes potassium hydroxide and/or sodium hydroxide；
Preferably, the mass ratio of step (a) mantoquita and step (b) palladium chloride is (20~70): 1；
Preferably, the mass ratio of step (a) mantoquita and step (b) glucose is (0.6~0.9): 1；
Preferably, step (b) reaction carries out under water bath condition；
Preferably, the bath temperature is 60~90 DEG C；
Preferably, the water bath time is 2~4h.
7. according to the described in any item preparation methods of claim 4-6, which is characterized in that step (1) the cuprous oxide dispersion
The solvent of liquid includes water and ethyl alcohol；
Preferably, the volume ratio of the water and ethyl alcohol is (0.5~2): 1；
Preferably, the mass ratio of step (1) the cuprous nano frame and nickel salt and cobalt salt is (0.8~1.2): 1；
Preferably, step (1) described nickel salt includes the group of any one in nickel nitrate, nickel chloride or nickel sulfate or at least two
It closes；
Preferably, step (1) described cobalt salt includes the group of any one in cobalt nitrate, cobalt chloride or cobaltous sulfate or at least two
It closes；
Preferably, the mass ratio of step (1) nickel salt and cobalt salt is (0.2~5): 1；
Preferably, step (1) described mixed liquor further includes surfactant；
Preferably, the surfactant includes polyvinylpyrrolidone and/or lauryl sodium sulfate；
Preferably, the mass ratio of the surfactant and step (1) described cuprous nano frame is (30~35): 1；
Preferably, step (1) described mixed liquor obtains stir process.
8. according to the described in any item preparation methods of claim 4-7, which is characterized in that step (2) described thiosulfate is molten
The concentration of liquid is 0.5~1.5mol/L；
Preferably, the adding manner of step (2) described thiosulfate solution is to be added dropwise；
Preferably, the molar ratio of step (2) thiosulfate and step (1) described cuprous nano frame be (70~
74):1；
Preferably, step (2) described thiosulfate includes any one in sodium thiosulfate, potassium thiosulfate or ATS (Ammonium thiosulphate)
Kind or at least two combination；
Preferably, step (2) reaction carries out under agitation；
Preferably, step (2) reaction temperature is 20~40 DEG C；
Preferably, step (2) reaction time is 10~20min；
Preferably, step (2) is described after reaction, through filtering, carrying out washing treatment, obtains nickel cobalt hydroxide nano frame.
9. according to the described in any item preparation methods of claim 4-8, which is characterized in that step (3) described precious metal salt includes
Any one in palladium salt, ruthenium salt, platinum salt or gold salt or at least two combination, preferably palladium salt；
Preferably, the palladium salt includes the combination of any one in chlorine palladium acid sodium, potassium chloropalladate or chlorine palladium acid or at least two；
Preferably, the mass ratio of step (3) precious metal salt and nickel cobalt hydroxide is (15~50): 1；
Preferably, step (3) described reducing agent includes sodium borohydride；
Preferably, the mass ratio of step (3) precious metal salt and reducing agent is (0.065~0.125): 1；
Preferably, step (3) reaction carries out under agitation；
Preferably, step (3) reaction temperature is 20~40 DEG C；
Preferably, step (3) reaction time is 5~15min；
Preferably, step (3) is described after reaction, is washed, is dried to reaction product, obtains noble metal support type nanometer
Frame catalyst.
10. a kind of purposes of the catalyst as described in claim any one of 1-3, which is characterized in that the catalyst is used as liberation of hydrogen
Catalysts.
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