CN109175347A - A kind of Au-Ir Nanoalloy, preparation method and the application as catalyst - Google Patents
A kind of Au-Ir Nanoalloy, preparation method and the application as catalyst Download PDFInfo
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- CN109175347A CN109175347A CN201811013887.2A CN201811013887A CN109175347A CN 109175347 A CN109175347 A CN 109175347A CN 201811013887 A CN201811013887 A CN 201811013887A CN 109175347 A CN109175347 A CN 109175347A
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- 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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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
Abstract
This application discloses a kind of Au-Ir Nanoalloy, partial size is 5~10nm；The molar ratio of Au and Ir in the Au-Ir Nanoalloy are as follows: 1:3~9:1.The particle size of the Au-Ir Nanoalloy is small, has great specific surface area and more active site, the pattern of Au-Ir Nanoalloy is adjustable, and different selectivity of product is shown in electro-catalysis carbon dioxide.
Description
Technical field
This application involves a kind of Au-Ir Nanoalloy, preparation method and as the application of catalyst, belong to nano material
Synthesis field.
Background technique
Since 21 century, with the large-scale use of fossil fuel, CO has been caused2Excessive emissions, while energy crisis
Also to increasingly sharpen, greatly affected the survival and development of people, old friends make great efforts to develop various satisfactory new energy,
To reduce the dependence to fossil fuel.CO2Rich reserves on earth, nonhazardous, if by CO2It is each for synthesizing as carbon source
The small organic molecule of the high economic value added of kind, such as: carbon monoxide (CO), formic acid (HCOOH), methanol (CH3OH), methane (CH4) etc.
Workable renewable resource.This not only reduces CO2Accumulation in an atmosphere, and various workable fuel can be generated
With useful industrial chemistry raw material, solves problem of energy crisis, form CO2- the energy-CO2Benign cycle, therefore by
The extensive concern of all circles is arrived.Electrochemistry CO2Reduction, can effectively generate hydrocarbon and alcohols at ambient temperature and pressure
Deng with the very various application potential of product distribution.Metal Au catalyst has CO2It is selectively converted to the ability of CO,
Numerous researchers have been attracted to pay close attention to.But when reducing due to Au nano-particles size, total current density sharp increases,
And CO yield slowly increases and hydrogen is skyrocketed through, so that CO2The faradic efficiency of reduction declines.Due in small gold
There are fairly large number of low harmony site, CO on nanoparticle2Reduction and HER are promoted.Therefore, the present invention passes through introducing
Second of metal Ir, causes to strain, and changes electronic structure and changes to influence the interaction between surface atom and reactant
The selectivity of change catalyzer, when being formed simultaneously alloy, some atom site is likely to form vacancy, these defect sites become
Active site improves the activity of metal nanoparticle.Electrochemical catalysis CO2The product of reduction can pass through the shape of change catalyst
Looks adjust, this represents has substantial worth for actual industrial application
Au has excellent electrochemical catalysis CO2Reduction activation, but Au is one of element rare in the earth's crust, so such as
What reduces its dosage and improves its catalytic capability as far as possible into a great problem.More and more people begin through various in recent years
Method such as adjusts the size of gold nano grain and shape improves catalytic activity, but with the reduction of Au nano-particles size, always
Current density sharp increase, hydrogen is skyrocketed through, and CO yield slowly increases, so that CO2The faraday of reduction is imitated
Rate decline.And gold is easy to grow up to bulky grain in gold nano catalyst preparation process, so that specific surface area reduces, reaction active site
Point cannot sufficiently expose, and violate with the original intention for the dosage for reducing noble metal.
Different from Au, Ir nucleation barrier is low, is easily formed little particle, but be difficult to obtain pattern with conventional chemical synthesis method
Controllable Ir nano particle.According to phasor rule, when being lower than 1100 DEG C, Au and Ir are immiscible, and low-temp reaction is difficult to form conjunction
Gold.Since Au, Ir reduction potential difference are big, Au is easy reduction, and the energy barrier that Au grows up is far below the energy barrier for forming AuIr alloy,
It is difficult to obtain the AuIr Nanoalloy of morphology controllable with conventional method.The synthesis of the AuIr Nanoalloy of morphology controllable at present is also not
It appears in the newspapers.
Summary of the invention
According to the one aspect of the application, a kind of Au-Ir Nanoalloy, the particle of the Au-Ir Nanoalloy are provided
Size is small, has great specific surface area and more active site, the pattern of catalyst is adjustable, in electro-catalysis carbon dioxide
Show different selectivity of product.
The partial size of the Au-Ir Nanoalloy is 5~10nm；
Mole of Au and Ir in the Au-Ir Nanoalloy are as follows: 1:3~9:1.
Optionally, the morphology controllable of the Au-Ir Nanoalloy.
Optionally, the crystal face of the Nanoalloy includes at least one of (111) crystal face, (200) crystal face.
Optionally, the pattern of the Au-Ir alloy includes Au-Ir duplex metal nano granule, Au-Ir bimetal nano octahedral
Body, Au-Ir bimetal nano cut end octahedron, Au-Ir bimetal nano cube.
Optionally, the crystal face of the Au-Ir duplex metal nano granule includes (111) crystal face of Au-Ir alloy；
The octahedral crystal face of Au-Ir bimetal nano includes (111) crystal face of Au-Ir alloy；
The Au-Ir bimetal nano cuts (111) crystal face that the octahedral crystal face in end includes Au-Ir alloy and (200) are brilliant
Face；
The crystal face of the Au-Ir bimetal nano cube includes (111) crystal face of Au-Ir alloy.
Optionally, the particular crystal plane of the Au-Ir duplex metal nano granule is (111) crystal face of Au-Ir alloy；
The octahedral particular crystal plane of Au-Ir bimetal nano is (111) crystal face of Au-Ir alloy；
The Au-Ir bimetal nano cuts (111) crystal face and (200) that the octahedral particular crystal plane in end is Au-Ir alloy
Crystal face；
The particular crystal plane of the Au-Ir bimetal nano cube is (111) crystal face of Au-Ir alloy.
" particular crystal plane " refers to that the Au-Ir Nanoalloy passes through control reaction condition, the Au-Ir of morphology controllable obtained
Nanoalloy, the desired crystal face exposed.
Optionally, the surface of the Au-Ir duplex metal nano granule is mainly (111) crystal face of Au-Ir alloy；
The octahedral surface of Au-Ir bimetal nano is mainly (111) crystal face of Au-Ir alloy；
The Au-Ir bimetal nano cuts (111) crystal face and (200) that the octahedral surface in end is mainly Au-Ir alloy
Crystal face；
The surface of the Au-Ir bimetal nano cube is mainly (111) crystal face of Au-Ir alloy.
As an implementation, a series of Au-Ir bimetal nano catalyst of morphology controllables, including Au-Ir are prepared
Duplex metal nano granule, Au-Ir bimetal nano is octahedra, and Au-Ir bimetal nano cuts end octahedron, and Au-Ir bimetallic is received
Rice cube.PVP (polyvinylpyrrolidone) and halide ion (Br-) are used as face selective agent, pass through accurate control plane selective agent
Concentration the Au-Ir bimetal nano catalyst with different-shape can be obtained, for particle size in 5-10nm, this kind of material can
For electro-catalysis CO2Reduction reaction.
According to further aspect of the application, the preparation method of Au-Ir Nanoalloy described in one kind is provided, is broken
In traditional phasor, the immiscible rule of solid-state Au, Ir.Wherein, select solvent oleyl amine as reducing agent, at high temperature to Au salt with
Ir salt carries out coreduction, Au-Ir alloy nanoparticle is prepared, while oleyl amine is used as surfactant again, can be effective
Control the size of alloy nanoparticle.PVP (polyvinylpyrrolidone) can effectively control Au in forming core and growth process
The growth of grain changes energy barrier and the energy barrier for forming AuIr alloy that Au grows up, available Au-Ir alloy nanoparticle.Halogen
Plain ion (Br-) it is used as face selective agent, by adjusting the type of metal precursor salt and halogen ion concentration is available has
The alloy nano catalyst of different-shape and performance.The catalyst has specific surface area high, and preparation condition is milder, catalytic effect
The advantages that preferable.The present invention is using oleyl amine as surfactant and reducing agent, PVP (polyvinylpyrrolidone) and halide ion
(Br-) it is used as face selective agent, synthesize the Au-Ir bimetal nano catalyst of morphology controllable and is used for electro-catalysis carbon dioxide also
It is former.Pass through the available alloy nano catalysis with different-shape of the type and halogen ion concentration that adjust metal precursor salt
Agent shows different selectivity of product to electro-catalysis carbon dioxide reduction.This method has synthesis simply, easy to operate, answers
The features such as wide with range, and preparation condition is milder, method is simple, and without special equipment, cost is cheaper.
The preparation method of the Au-Ir Nanoalloy, which is characterized in that by metal precursor salt containing Ir, Au
The mixture of metal precursor salt and reducing agent, under the conditions of inert atmosphere, coreduction reaction is obtained Au-Ir nanometers described
Alloy.
The method, by the addition of surfactant, the energy barrier for adjusting Au and Ir forming core and growing up, so that Au and Ir is total
Reduction, the adjustable AuIr alloy for obtaining morphology controllable change simultaneously as the introducing of second of metal Ir, causes to strain
Electronic structure changes the selectivity of catalyst to influence the interaction between surface atom and reactant.
The preparation method of the Au-Ir Nanoalloy, which is characterized in that by metal precursor salt containing Ir, Au
Metal precursor salt, oleyl amine raw material mixing ultrasonic disperse obtain mixture；The mixture is heated, oleyl amine is as reducing agent
Coreduction is carried out to Au salt and Ir salt, the Au-Ir Nanoalloy is prepared.
Optionally, the preparation method of the Au-Ir Nanoalloy, using the method for coreduction, by the metal precursor of Ir
The metal precursor salt of salt and Au are added in reaction vessel simultaneously, and solvent oleyl amine is as reducing agent at high temperature to Au salt and Ir salt
Coreduction is carried out, AuIr alloy nanoparticle is prepared.
Optionally, contain solvent in the mixture；The solvent is selected from oleyl amine, the mixture of oleyl amine and oleic acid, oleyl amine
One of with the mixture of octadecylene, wherein oleyl amine is simultaneously as the reducing agent reacted；
The additional amount of the reducing agent meets: the molar ratio of reducing agent oleyl amine and metal precursor salt is greater than 35:1；It is described
Metal precursor salt includes the metal precursor salt of Ir and the metal precursor salt of Au；
The metal precursor of the Au is selected from least one of tetra chlorauric acid trihydrate, acetic acid gold；
The metal precursor of the Ir selected from three chloride hydrate iridium, six chloro-iridic acids of hydration, in 2,4- pentanedionate iridium extremely
Few one kind；
The inert atmosphere is selected from least one of nitrogen, inert gas.
Preferably, the concentration of the metal precursor salt of Au is 0.5~10.5mg/ml in the mixture；
The concentration of the metal precursor of the Ir is 0.3~8mg/ml.
Optionally, the upper limit of the concentration of the metal precursor salt of the Au be selected from 10.5mg, 10mg, 9mg, 8mg/ml,
7mg/ml, 6mg/ml, 5mg/ml, 4mg/ml, 3mg/ml, 2mg/ml or 1mg/ml；Lower limit be selected from 1mg/ml, 0.9mg/ml,
0.8mg/ml, 0.7mg/ml, 0.6mg/ml or 0.5mg/ml.
Optionally, the upper limit of the concentration of the metal precursor salt of the Ir is selected from 8mg/ml, 7mg/ml, 6mg/ml, 5mg/
Ml, 4mg/ml, 3mg/ml, 2mg/ml or 1mg/ml；Lower limit be selected from 1mg/ml, 0.9mg/ml, 0.8mg/ml, 0.7mg/ml,
0.6mg/ml, 0.5mg/ml, 0.4mg/ml or 0.3mg/ml.
It optionally, further include at least one of surfactant, face selective agent in the mixture.
Optionally, the surfactant is selected from least one of oleyl amine, oleic acid；
Optionally, the face selective agent is selected from least one of PVP, the compound containing halide ion.
Optionally, the halide ion is Br-、I-, wherein it is preferred that Br-。
Optionally, the Br-From at least one of the compound with chemical formula shown in Formulas I:
Wherein, R1, R2, R3, R4Independently selected from one of alkyl.
Optionally, R1, R2, R3, R4Independently selected from C1~C4One of alkyl.
Optionally, the PVP be selected from molecular weight be one of 40000,55000, in mixture the concentration of PVP be 1~
10mg/ml；
The concentration of halide ion is 2~25mg/ml in the mixture.
Optionally, the temperature of the coreduction reaction is 150~250 DEG C, and the time of reaction is 30~300min.
Preferably, the temperature of the coreduction reaction is 200~220 DEG C.
Preferably, the time of the coreduction reaction is 60~120min.
Optionally, the upper limit of the temperature of the coreduction reaction is selected from 250 DEG C, 220 DEG C or 200 DEG C；Lower limit is selected from 200
DEG C, 180 DEG C or 150 DEG C.
Optionally, the upper limit of the time of the coreduction reaction is selected from 120min, 100min or 80min；Lower limit is selected from
80min, 70min or 60min.
Optionally, which comprises
(S11) the raw material mixing ultrasonic disperse of the metal precursor salt containing Ir, the metal precursor salt of Au, oleyl amine is obtained
To mixture；In the mixture concentration of the metal precursor salt of Ir be 0.3~8mg/mL, the metal precursor salt of Au it is dense
Degree is 0.5~10.5mg/mL；
(S12) mixture obtained in step (S11) is heated to 150~250 DEG C, 30~300min of isothermal reaction；
(S13) after reaction, it is naturally cooling to room temperature, is separated, washs, is dried to obtain the Au-Ir Nanoalloy.
Optionally, which comprises
(S21) the metal precursor salt containing Ir, the metal precursor salt of Au, PVP and face selective agent are contained into halide ion
Compound be proportionally added in oleyl amine, ultrasonic disperse obtain mixture；
The gold presoma, iridium precursor salt, the compound of PVP and face selective agent containing halide ion are in the mixture
Mass concentration be respectively 0.5~10.5mg/ml, 0.3~8mg/ml, 1~10mg/ml and 2~25mg/ml；
(S22) mixture obtained in (S21) step is placed in the oil bath for be preheated to 150-250 DEG C and reacts 30-
300min；
(S23) after reaction, it is down to room temperature, after obtained product centrifugation, washing, oven drying is to get the Au-Ir
Nanoalloy.
Optionally, the upper limit of mass concentration of the PVP in the mixture is selected from 10mg/ml, 9mg/ml, 8mg/
Ml, 7mg/ml or 6mg/ml；Lower limit is selected from 5mg/ml, 4mg/ml, 3mg/ml, 2mg/ml or 1mg/ml.
Optionally, the upper limit choosing of mass concentration of the compound of the face selective agent containing halide ion in the mixture
From 25mg/ml, 22mg/ml, 20mg/ml, 18mg/ml, 15mg/ml, 12mg/ml, 10mg/ml, 9mg/ml, 8mg/ml, 7mg/
Ml or 6mg/ml；Lower limit is selected from 5mg/ml, 4mg/ml, 3mg/ml or 2mg/ml.
Optionally, the metal precursor salt of Ir described in step (S11) is selected from three chloride hydrate iridium (III), hydration chlordene
At least one of iridium (IV) acid, 2,4- pentanedionate iridium (III).
Preferably, step (S12) are as follows: mixture obtained in step (S11) is heated to 200~220 DEG C, isothermal reaction
60~120min.
Optionally, the solvent of washing described in step (S13) is the mixed solution of water, ethyl alcohol, hexamethylene, acetone；
Dry temperature described in step (S13) is 30~80 DEG C, and the time of the drying is not less than 12h.
Preferably, temperature dry described in step (S13) is 50~70 DEG C.
As an implementation, using oleyl amine as surfactant and reducing agent preparation Au-Ir alloy nano catalysis
The method of agent and its application in electro-catalysis carbon dioxide reduction.Using the method for coreduction, by the metal precursor salt of Ir
Be added in reaction vessel simultaneously with the metal precursor salt of Au, solvent oleyl amine as reducing agent at high temperature to Au salt and Ir salt into
Au-Ir alloy nanoparticle is prepared in row coreduction, while oleyl amine is used as surfactant to control alloy nanoparticle again
Pattern.PVP (polyvinylpyrrolidone) and halide ion (Br-) it is used as face selective agent, by adjusting metal precursor salt
Type and the available alloy nano catalyst with different-shape and performance of halogen ion concentration.Difference prepared by the present invention
The Au-Ir alloy nano catalyst of pattern shows different selectivity of product to electro-catalysis carbon dioxide reduction.
As another embodiment, the Au-Ir Nanoalloy is Au-Ir duplex metal nano granule.
Optionally, the metal precursor salt of the Ir is three chloride hydrate iridium, and the metal precursor salt of the Au is tetrachloro
Auric acid trihydrate.
As another embodiment, raw material described in step (S11) includes face selective agent；The face selective agent includes poly-
Vinylpyrrolidone and halide ion Br-；Preferably, the halide ion Br-From compound shown in Formulas I:
Wherein, R1, R2, R3, R4Independently selected from alkyl；Preferably, the halide ion Br-From tetraethylammonium bromide.
Optionally, the concentration of polyvinylpyrrolidone described in step (S11) described mixture is 1~10mg/mL, described
Halide ion Br-Concentration be 2~25mg/mL.
As another embodiment, the Au-Ir Nanoalloy is that Au-Ir bimetal nano is octahedra；The mixing
The concentration of the metal precursor salt of Ir is 1.0mg/mL in object, and the concentration of the metal precursor salt of Au is 1.02mg/mL, described poly-
The concentration of vinylpyrrolidone is 2.86mg/mL, the halide ion Br-Concentration be 3.6mg/mL.
Optionally, the metal precursor salt of the Ir is three chloride hydrate iridium, and the metal precursor salt of the Au is tetrachloro
Auric acid trihydrate.
The Au-Ir Nanoalloy is that Au-Ir bimetal nano cuts end octahedron；The metal front of Ir in the mixture
The concentration of body salt is 1.35mg/mL, and the concentration of the metal precursor salt of Au is 1.19mg/mL, the polyvinylpyrrolidone
Concentration is 1.11mg/mL, the halide ion Br-Concentration be 4.2mg/mL.
Optionally, the metal precursor salt of the Ir is hydration chlordene iridium (IV) acid, and the metal precursor salt of the Au is
Tetra chlorauric acid trihydrate.
The Au-Ir Nanoalloy is Au-Ir bimetal nano cube；The metal precursor salt of Ir in the mixture
Concentration be 1.35mg/mL, the concentration of the metal precursor salt of Au is 1.19mg/mL, the concentration of the polyvinylpyrrolidone
For 1.11mg/mL, the halide ion Br-Concentration be 14mg/mL.
Optionally, the metal precursor salt of the Ir is hydration chlordene iridium (IV) acid, and the metal precursor salt of the Au is
Tetra chlorauric acid trihydrate.
As an implementation, the preparation method of the Au-Ir duplex metal nano granule includes:
(1) by three chloride hydrate iridium, tetra chlorauric acid trihydrate is added to according to a certain percentage in a certain amount of oleyl amine, envelope
Mouthful, ultrasonic disperse obtains mixture；
(2) mixture solution prepared by step (1) is put into the oil bath for being preheated to certain temperature, N2Under atmosphere, instead
Certain time is answered to obtain product；
(3) cooled to room temperature will obtain product centrifugation, be washed with ethyl alcohol, hexamethylene mixed solution；
(4) it is dried overnight, obtains Au-Ir duplex metal alloy nano particle of the present invention.
The gold precursor salt, iridium precursor salt, the concentration essence of PVP (polyvinylpyrrolidone) and halide ion (Br-)
Really control, to prepare the Au-Ir bimetal nano catalyst of different-shape
The different iridium precursor salts of selection described in the step (1) prepare the Au-Ir bimetal nano catalysis of different-shape
Agent.
Optionally, in the step (1) by golden precursor salt, iridium precursor salt, PVP and face selective agent Br- compound
It is added according to certain mass ratio.The gold precursor salt, iridium precursor salt, PVP and face selective agent Br- compound described
Mass concentration in mixture is respectively 0.5-10.5mg/ml, 0.3-8mg/ml, 1-10mg/ml, 2-25mg/ml.
Optionally, the catalyst is used for electro-catalysis CO2Reduction reaction.
The application has studied the influence of electronic structure and pattern to catalyst choice, the catalyst " different crystal faces "
The pattern for only needing to change metal nanoparticle can be realized, and changes electronic structure by forming alloy, will have a direct impact on catalysis
The electro-catalysis selectivity of agent, the Au-Ir duplex metal nano granule of different-shape show different carbon dioxide selectivities.
According to the another aspect of the application, a kind of catalyst is provided, which is characterized in that close containing the Au-Ir nanometer
At least one of gold, the Au-Ir Nanoalloy prepared according to the method.
Optionally, the catalyst is used for electro-catalysis CO2Reduction reaction.
Optionally, described to be used for electro-catalysis CO2The preparation method of the catalyst of reduction reaction includes:
By the Au-Ir Nanoalloy, carbon black, ultrasonic disperse is uniform in etoh solvent and isopropanol, obtains mixture B；
Perfluorinated resin solution is added in mixture B, ultrasound obtains the catalyst.
In the application, the solvent is selected in the mixture of the mixture of oleyl amine, oleyl amine and oleic acid, oleyl amine and octadecylene
It is a kind of.Wherein preferred oleyl amine, purity are 50%~90%, and purity 50% has met requirement of experiment, preferably solvent with high purity.
In the application, PVP (polyvinylpyrrolidone) molecular formula is as follows, wherein preferably 40000 He of molecular weight
55000 PVP.
In the application, the face selective agent Br-Selected from compound shown in following molecular formula, R1, R2, R3 are identical with R4 or not
Together, it is independently from each other alkyl.
R in the application1, R2, R3, R4Independently selected from C1~C4One of alkyl."C1~C4" refer to the carbon that group is included
Atomicity.
In the application, " alkyl " is to be formed by group by losing any one hydrogen atom on alkane compound molecule.
The beneficial effect that the application can generate includes:
1) Au-Ir Nanoalloy provided herein can be adjusted by changing the ratio of iridium presoma and golden presoma
Control the element ratio of Au and Ir；
2) Au-Ir Nanoalloy provided herein can be adjusted by changing metal precursor and protectant ratio
Control the pattern of Au-Ir Nanoalloy；
3) Au-Ir Nanoalloy provided herein, particle size is small, has great specific surface area and active sites
Point.
Detailed description of the invention
Fig. 1 is the Au-Ir Nanoalloy of the application preparation, and wherein a is Au-Ir bimetal nano prepared by embodiment 1
The transmission electron microscope photo of grain, b are the high-resolution-ration transmission electric-lens photo of Au-Ir duplex metal nano granule prepared by embodiment 1, and c is
The octahedral transmission electron microscope photo of Au-Ir bimetal nano prepared by embodiment 2, d are Au-Ir bimetallic prepared by embodiment 2
The octahedral high-resolution-ration transmission electric-lens photo of nanometer, e are that Au-Ir bimetal nano section end prepared by embodiment 3 is octahedral
Electromicroscopic photograph is penetrated, f is that Au-Ir bimetal nano prepared by embodiment 3 cuts the octahedral high-resolution-ration transmission electric-lens photo in end, and g is
The transmission electron microscope photo of Au-Ir bimetal nano cube prepared by embodiment 4, h are Au-Ir bimetallic prepared by embodiment 4
The high-resolution-ration transmission electric-lens photo of nanocube；
Fig. 2 is that the catalyst of the application preparation is used for electro-catalysis CO2The electrochemical property test of reduction reaction is as a result, wherein
A is the CO of Au-Ir duplex metal nano granule prepared by embodiment 12Reduzate selectivity, abscissa-voltage, unit is volt
(V), relative to standard hydrogen electrode；Ordinate-faradic efficiency, unit %, b are that Au-Ir bimetallic prepared by embodiment 1 is received
The electro-catalysis CO of rice grain2The portion of electrical current density of reduction reaction, abscissa-voltage, unit is volt (V), relative to standard
Hydrogen electrode；Ordinate-current density, unit are milliampere (mA/cm every square centimeter2), c is the bis- gold of Au-Ir prepared by embodiment 2
Belong to the octahedral CO of nanometer2Reduzate selectivity, abscissa-voltage, unit is volt (V), relative to standard hydrogen electrode；It is vertical
Coordinate-faradic efficiency, unit %, d are the octahedral electro-catalysis CO of Au-Ir bimetal nano prepared by embodiment 22Reduction
The portion of electrical current density of reaction, abscissa-voltage, unit is volt (V), relative to standard hydrogen electrode；Ordinate-electric current is close
Degree, unit are milliampere (mA/cm every square centimeter2), e is that Au-Ir bimetal nano prepared by embodiment 3 cuts the octahedral CO in end2
Reduzate selectivity, abscissa-voltage, unit is volt (V), relative to standard hydrogen electrode；Ordinate-faradic efficiency,
Unit is %, and f is that Au-Ir bimetal nano prepared by embodiment 3 cuts the octahedral electro-catalysis CO in end2The part electricity of reduction reaction
Current density, abscissa-voltage, unit is volt (V), relative to standard hydrogen electrode；Ordinate-current density, unit are milliampere
(mA/cm every square centimeter2)。
Specific embodiment
The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.
Unless otherwise instructed, the raw material in embodiments herein and solvent are bought by commercial sources, specific raw material
It see the table below:
1 experimental raw of table
Analysis method is as follows in embodiments herein:
Morphology characterization is carried out using FEI Tecnai G2F20 transmission electron microscope.
The preparation method of embodiment 1:Au-Ir duplex metal nano granule
(1) by the three chloride hydrate iridium of 0.1mmol, the tetra chlorauric acid trihydrate of 0.1mmol is added to two mouthfuls of 100ml burnings
In bottle, adds 35ml oleyl amine ultrasound 60min and obtain mixture A.
(2) mixture A is put into the oil bath for being preheated to 200 DEG C, N2Under atmosphere, reaction 1h obtains product B.
(3) cooled to room temperature will obtain product B centrifugation (12000 revs/min), with ethyl alcohol, hexamethylene mixed solution
(ethyl alcohol, hexamethylene volume ratio be 1:1) washing 6 times.
(4) 70 DEG C are dried overnight to obtain Au-Ir duplex metal nano granule of the present invention.
The octahedral preparation method of embodiment 2:Au-Ir bimetal nano
(1) by the three chloride hydrate iridium of 0.1mmol, the tetra chlorauric acid trihydrate of 0.1mmol, 0.6mmol tetrem bromide
Change ammonium, 100mg PVP (molecular weight 40000) is added in 100ml two mouth flask, adds 35ml oleyl amine ultrasound 60min, stir
It mixes 4h and obtains mixture A.
(2) mixture A is put into the oil bath for being preheated to 220 DEG C, N2Under atmosphere, reaction 1h obtains product B.
(3) cooled to room temperature will obtain product B centrifugation (12000 revs/min), with water, ethyl alcohol, hexamethylene and acetone
Mixed solution (water, ethyl alcohol, hexamethylene and acetone volume ratio be 1:4:1:2) washing 14 times.
(4) 70 DEG C are dried overnight to obtain Au-Ir bimetal nano octahedron of the present invention.
Embodiment 3:Au-Ir bimetal nano cuts the octahedral preparation method in end
(1) by hydration chlordene iridium (IV) acid of 0.1mmol, the tetra chlorauric acid trihydrate of 0.1mmol, 0.6mmol tetrem
Base ammonium bromide, 33.3mg PVP (molecular weight 55000) are added in 100ml two mouth flask, add 30ml oleyl amine ultrasound
60min, stirring 4h obtain mixture A.
(2) mixture A is put into the oil bath for being preheated to 220 DEG C, N2Under atmosphere, reaction 1h obtains product B.
(3) cooled to room temperature will obtain product B centrifugation (12000 revs/min), with water, ethyl alcohol, hexamethylene and acetone
Mixed solution (ethyl alcohol, ether, n-hexane and acetone volume ratio be 5:5:3:5) washing 12 times.
(4) 70 DEG C are dried overnight to obtain Au-Ir bimetal nano of the present invention section end octahedron.
The preparation method of embodiment 4:Au-Ir bimetal nano cube
(1) by hydration chlordene iridium (IV) acid of 0.1mmol, the tetra chlorauric acid trihydrate of 0.1mmol, 2.0mmol tetrem
Base ammonium bromide, 33.3mg PVP (molecular weight 55000) are added in 100ml two mouth flask, add 30ml oleyl amine ultrasound
60min, stirring 4h obtain mixture A.
(2) mixture A is put into the oil bath for being preheated to 220 DEG C, N2Under atmosphere, reaction 1h obtains product B.
(3) cooled to room temperature will obtain product B centrifugation (12000 revs/min), with water, ethyl alcohol, hexamethylene and acetone
Mixed solution (ethyl alcohol, ether, n-hexane and acetone volume ratio be 5:5:3:5) washing 12 times.
(4) 70 DEG C are dried overnight to obtain Au-Ir bimetal nano cube of the present invention.
The preparation method of embodiment 5:Au-Ir duplex metal nano granule
Concrete operations with embodiment 1, the difference is that, the three chloride hydrate iridium of 0.03mmol are added in step (1).
The preparation method of embodiment 6:Au-Ir duplex metal nano granule
Concrete operations with embodiment 1, the difference is that, the three chloride hydrate iridium of 0.3mmol are added in step (1).
The preparation method of embodiment 7:Au-Ir duplex metal nano granule
Concrete operations with embodiment 1, the difference is that, the tetra chlorauric acid three that 0.5mmol is added in step (1) is hydrated
Object.
The preparation method of embodiment 8:Au-Ir duplex metal nano granule
Concrete operations with embodiment 1, the difference is that, the tetra chlorauric acid three that 0.9mmol is added in step (1) is hydrated
Object.
The preparation method of embodiment 9:Au-Ir duplex metal nano granule
Concrete operations with embodiment 1, the difference is that, mixture A is put into step (2) and is preheated to 150 DEG C of oil
In bath, N2Under atmosphere, reaction 300min obtains product B.
The preparation method of embodiment 10:Au-Ir duplex metal nano granule
Concrete operations with embodiment 1, the difference is that, mixture A is put into step (2) and is preheated to 250 DEG C of oil
In bath, N2Under atmosphere, reaction 30min obtains product B.
The preparation method of embodiment 11:Au-Ir bimetal nano catalyst
(1) the Au-Ir duplex metal nano granule that will be prepared in 4mg embodiment 1,4mgVulcan XC-72 carbon black add
Enter into 10ml vial, add 1ml ethyl alcohol, 1ml isopropanol, ultrasonic 3h makes it be uniformly dispersed to obtain mixture A.
(2) 80 μ L are added in mixture APerfluorinated resin solution, ultrasonic 1h obtain Au-Ir bimetallic
Nanocatalyst is named as CAT1#.
Embodiment 12:Au-Ir bimetal nano is octahedra, and Au-Ir bimetal nano cuts end octahedron, Au-Ir bimetallic
The preparation of nanocube catalyst series
All steps are identical as embodiment 11, and in addition to the Au-Ir bimetal nano for being separately added into 4mg is octahedra, Au-Ir is bis-
Metal nano cuts end octahedron, and Au-Ir bimetal nano cube respectively obtains CAT2#, CAT3#, CAT4#.
The morphology characterization of embodiment 13:Au-Ir Nanoalloy
Morphology characterization is carried out to Au-Ir Nanoalloy prepared by embodiment 1~implementation 10, typical TEM figure is such as Fig. 1 institute
Show, Fig. 1 is the Au-Ir duplex metal nano granule that case study on implementation 1,2,3,4 provides, and Au-Ir bimetal nano is octahedra, Au-Ir
Bimetal nano cuts end octahedron, the transmission electron microscope photo of Au-Ir bimetal nano cube.It can be seen that being closed from Fig. 1 a
At nano particle diameter be about 5 rans, Fig. 1 b high-resolution photo shows that its spacing of lattice is about that 0.227-0.230 receives
Rice shows catalyst surface largely and is (111) crystal face of Au-Ir alloy.Scheme c, d is that Au-Ir bimetal nano is octahedral
Transmission electron microscope photo, high-resolution photo show that its spacing of lattice is about 0.228 nanometer, show that catalyst surface is largely Au-
Octahedral (111) crystal face of Ir alloy nano.Scheme e, f is that Au-Ir bimetal nano cuts the octahedral transmission electron microscope photo in end, high
It differentiates photo and shows that its spacing of lattice is about 0.230 nanometer and 0.202 nanometer, showing catalyst surface largely is that Au-Ir is closed
Gold nano, which is cut, holds octahedral (111) and (200) crystal face.Scheme g, h is that the transmission electron microscope of Au-Ir bimetal nano cube shines
Piece, high-resolution photo show that its spacing of lattice is about 0.228 nanometer, and showing catalyst surface largely is Au-Ir alloy nano
(111) crystal face of cube.The Au-Ir that Au-Ir Nanoalloy prepared by 5~embodiment of embodiment 10 is prepared with embodiment 1 receives
The pattern of meter He Jin is similar.
Embodiment 14: electro-catalysis CO2The reaction step of reduction
The preparation of electrode: electro-chemical test is carried out in dual chamber H-type electrolytic cell.Working electrode is to take a certain amount of embodiment 11
With the catalyst mixed liquid prepared in embodiment 12, drip in carbon paper surface (carbon paper electrode, carbon paper size 1cm*1cm, area
1cm2), drying is prepared, and platinum guaze is to electrode, reference electrode Ag/AgCl.
The quality of the catalyst taken needs to refer to the mass percent of Au-Ir in different catalysts, and final load is made to exist
The content of metal Au-Ir is 30 μ g/cm in the catalyst of electrode2。
Electrochemical property test: first in 0.5M KHCO3Electrolyte in lead to CO2Half an hour makes its CO2Saturation, ventilation speed
Degree is 30ml/min, and cyclic voltammetry scan, scanning speed 100mVs are then carried out in the solution-1, scanning range 0.1
~-0.6V, scanning circle number 200 enclose, and the effect of the step is catalyst surface to be cleaned and played certain activation.
Later in CO20.5M KHCO under atmosphere3Its constant pressure product is tested in solution to characterize the electro-catalysis CO of catalyst2Reproducibility
Can, constant pressure current potential is -0.4~-1.2V, takes a current potential every 0.1V.
Electro-catalysis CO2Product measurement: gas-phase product is surveyed by gas Chromatographic Determination, liquid product by nuclear-magnetism and ion chromatography
It is fixed.
It is standard hydrogen electrode that the above scanning range, which chooses institute's reference,.
Fig. 2 is respectively the electrochemistry of catalyst provided by CAT1#, CAT2#, CAT3# in embodiment 11 and embodiment 12
Performance test: CO2Reduzate selectivity and portion of electrical current density.As can be seen from the figure the Au-Ir synthesized by the present invention is bis-
Metal nano catalyst, including nano particle, nanometer is octahedra, nanometer cuts end octahedron, and different-shape exposes different crystalline substances
Face shows different catalytic performance: activity and selectivity.Fig. 2 a is the CO of catalyst CAT1# prepared by embodiment 112Reduction
Selectivity of product, relative to standard hydrogen electrode, CO faradic efficiency reaches highest when -0.6V, is 78.4%, with overpotential liter
Height, CO are selectively reduced, and evolving hydrogen reaction selectively increases；B is the electro-catalysis CO of catalyst CAT1# prepared by embodiment 112Also
The portion of electrical current density of original reaction, CO before intersection point2CO dominance is reverted to, evolving hydrogen reaction is dominant after intersection point；C is to implement
The CO of catalyst CAT2# prepared by example 122Reduzate selectivity, product includes CO, hydrogen and formic acid.Relative to standard hydrogen electricity
Pole, product all hydrogen when -0.4V, with the raising of overpotential, formic acid faradic efficiency is increased, and when -0.8V reaches highest,
It is 24%, continues growing overpotential, formic acid selectively reduces, and hydrogen selective increases；D is catalyst prepared by embodiment 12
The electro-catalysis CO of CAT2#2The portion of electrical current density of reduction reaction, the portion of electrical current density of CAT2# are apparently higher than the part of CAT1#
Current density illustrates the activity of catalyst CAT2# better than CAT1#；E is the CO of catalyst CAT3# prepared by embodiment 122Reduction
Selectivity of product, relative to standard hydrogen electrode, the faradic efficiency of CO and hydrogen is 50% when -0.5V, with overpotential liter
Height, CO are selectively increased, and -0.7V reaches maximum value, are 66.7%, and until -1.0V, CO selectivity is still dominant；F is embodiment
The electro-catalysis CO of the catalyst CAT3# of 12 preparations2The portion of electrical current density of the portion of electrical current density of reduction reaction, CAT3# is obvious
Portion of electrical current density higher than CAT1# illustrates the activity of catalyst CAT3# better than CAT1#.
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (10)
1. a kind of Au-Ir Nanoalloy, which is characterized in that the partial size of the Au-Ir Nanoalloy is 5~10nm；
The molar ratio of Au and Ir in the Au-Ir Nanoalloy are as follows: 1:3~9:1.
2. Au-Ir Nanoalloy according to claim 1, which is characterized in that the crystal face of the Nanoalloy includes (111)
At least one of crystal face, (200) crystal face；
Preferably, the pattern of the Au-Ir alloy include Au-Ir duplex metal nano granule, Au-Ir bimetal nano it is octahedra,
Au-Ir bimetal nano cuts end octahedron, Au-Ir bimetal nano cube；
Preferably, the crystal face of the Au-Ir duplex metal nano granule includes (111) crystal face of Au-Ir alloy；
The octahedral crystal face of Au-Ir bimetal nano includes (111) crystal face of Au-Ir alloy；
The Au-Ir bimetal nano cuts (111) crystal face and (200) crystal face that the octahedral crystal face in end includes Au-Ir alloy；
The crystal face of the Au-Ir bimetal nano cube includes (111) crystal face of Au-Ir alloy.
3. the preparation method of Au-Ir Nanoalloy of any of claims 1 or 2, which is characterized in that by the metal front containing Ir
Body salt, the metal precursor salt of Au and the mixture of reducing agent, under the conditions of inert atmosphere, coreduction reacts, described in acquisition
Au-Ir Nanoalloy.
4. according to the method described in claim 3, it is characterized in that, containing solvent in the mixture；The solvent is selected from oil
One of amine, the mixture of oleyl amine and oleic acid, oleyl amine and mixture of octadecylene, wherein the oleyl amine reduction as reaction simultaneously
Agent；
The additional amount of the reducing agent meets: the molar ratio of reducing agent oleyl amine and metal precursor salt is greater than 35:1；The metal
Precursor salt includes the metal precursor salt of Ir and the metal precursor salt of Au；
The metal precursor of the Au is selected from least one of tetra chlorauric acid trihydrate, acetic acid gold；
The metal precursor of the Ir is selected from three chloride hydrate iridium, six chloro-iridic acids of hydration, at least one in 2,4- pentanedionate iridium
Kind；
The inert atmosphere is selected from least one of nitrogen, inert gas.
Preferably, the concentration of the metal precursor salt of Au is 0.5~10.5mg/ml in the mixture；
The concentration of the metal precursor of the Ir is 0.3~8mg/ml.
5. according to the method described in claim 3, it is characterized in that, further including surfactant, face selection in the mixture
At least one of agent；
Preferably, the surfactant is selected from least one of oleyl amine, oleic acid；
Preferably, the face selection solvent is selected from least one of PVP, the compound containing halide ion；
The halide ion is Br-、I-, wherein it is preferred that Br-；
Preferably, the Br-From at least one of the compound with chemical formula shown in Formulas I:
Wherein, R1, R2, R3, R4Independently selected from one of alkyl；
Preferably, R1, R2, R3, R4Independently selected from C1~C4One of alkyl.
Preferably, it is one of 40000,55000 that the PVP, which is selected from molecular weight, and the concentration of PVP is 1~10mg/ in mixture
ml；
The concentration of halide ion is 2~25mg/ml in the mixture.
6. according to the method described in claim 3, it is characterized in that, the temperature of coreduction reaction is 150~250 DEG C, instead
The time answered is 30~300min；
Preferably, the temperature of the coreduction reaction is 200~220 DEG C；
Preferably, the time of the coreduction reaction is 60~120min.
7. according to the method described in claim 3, it is characterized in that, which comprises
(S11) raw material of the metal precursor salt containing Ir, the metal precursor salt of Au, oleyl amine dispersion is mixed to be mixed
Object；The concentration of the metal precursor salt of Ir is 0.3~8mg/mL in the mixture, and the concentration of the metal precursor salt of Au is
0.5~10.5mg/mL；
(S12) mixture obtained in step (S11) is heated to 150~250 DEG C, 30~300min of isothermal reaction；
(S13) after reaction, it is naturally cooling to room temperature, is separated, washs, is dried to obtain the Au-Ir Nanoalloy.
8. according to the method described in claim 3, it is characterized in that, which comprises
(S21) by the change of metal precursor salt, PVP and face selective agent containing halide ion of the metal precursor salt containing Ir, Au
It closes object to be proportionally added in oleyl amine, ultrasonic disperse obtains mixture；
The metal precursor salt of the Au, the metal precursor salt of Ir, the compound of PVP and face selective agent containing halide ion are in institute
Stating the mass concentration in mixture is respectively 0.5~10.5mg/ml, 0.3~8mg/ml, 1~10mg/ml and 2~25mg/ml；
(S22) mixture obtained in (S21) step is placed in the oil bath for be preheated to 150-250 DEG C and reacts 30-300min；
(S23) after reaction, it is down to room temperature, after obtained product centrifugation, washing, oven drying is to get Au-Ir nanometers described
Alloy.
9. a kind of catalyst, which is characterized in that comprising Au-Ir Nanoalloy of any of claims 1 or 2, according to claim 3
At least one of the Au-Ir Nanoalloy being prepared to 8 described in any item methods.
10. catalyst according to claim 9, which is characterized in that the catalyst is used for electro-catalysis CO2Reduction reaction.
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