CN108746659A - A kind of flower-shaped AgPd Nanoalloys and preparation and application - Google Patents
A kind of flower-shaped AgPd Nanoalloys and preparation and application Download PDFInfo
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- CN108746659A CN108746659A CN201810555378.6A CN201810555378A CN108746659A CN 108746659 A CN108746659 A CN 108746659A CN 201810555378 A CN201810555378 A CN 201810555378A CN 108746659 A CN108746659 A CN 108746659A
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- agpd
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- palladium
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 107
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 28
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 14
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 14
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 14
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 49
- 150000004675 formic acid derivatives Chemical class 0.000 claims description 26
- 238000006555 catalytic reaction Methods 0.000 claims description 19
- 239000012153 distilled water Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000013019 agitation Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 150000002940 palladium Chemical class 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 229910003603 H2PdCl4 Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 3
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- XFTQRUTUGRCSGO-UHFFFAOYSA-N pyrazin-2-amine Chemical compound NC1=CN=CC=N1 XFTQRUTUGRCSGO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 113
- 239000000956 alloy Substances 0.000 abstract description 54
- 229910045601 alloy Inorganic materials 0.000 abstract description 54
- 238000007254 oxidation reaction Methods 0.000 abstract description 33
- 230000003647 oxidation Effects 0.000 abstract description 17
- 238000005286 illumination Methods 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000005518 electrochemistry Effects 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 229910021124 PdAg Inorganic materials 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- 238000002484 cyclic voltammetry Methods 0.000 description 27
- 238000006392 deoxygenation reaction Methods 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 12
- 239000000446 fuel Substances 0.000 description 11
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 10
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000000840 electrochemical analysis Methods 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 230000010287 polarization Effects 0.000 description 7
- 235000019253 formic acid Nutrition 0.000 description 6
- 229940101209 mercuric oxide Drugs 0.000 description 5
- 229910000474 mercury oxide Inorganic materials 0.000 description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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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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- 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
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- B22F1/0553—Complex form nanoparticles, e.g. prism, pyramid, octahedron
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
The present invention relates to a kind of flower-shaped AgPd Nanoalloys and preparation and application, it is to prepare a kind of flower-shaped PdAg nanometer alloy catalysts using solution co-reducing process, it is alloy element to introduce relatively inexpensive Ag, the use of ascorbic acid and hydrazine hydrate is reducing agent, using Apzc as pattern controlling agent, the average grain diameter for the AgPd nanometer alloy catalysts prepared is 320nm, favorable dispersibility, pattern is flower-shaped, wherein content silver-colored in AgPd nanometer alloy catalysts is 25~75%, the content of palladium is 25~75%, and the percentage is atomic percent.The electrochemistry specific surface area of flower-shaped AgPd nanometer alloy catalysts is 3.79~10.37m2/ g has excellent catalytic activity and stability, and the current density in 0.7V vs.RHE is 1.75~26.16mA/cm2.Under simulated solar illumination, the pure Pd and Ag that prepare50Pd50The oxidation peak current of nanometer alloy catalyst is respectively from 8.52mA/cm2It is increased to 9.11mA/cm2, and from 26.16mA/cm2It is increased to 30.97mA/cm2。
Description
Technical field
The invention belongs to electro-catalysis and photocatalysis technology field, it is related to a kind of flower-shaped AgPd Nanoalloys and preparation and use
A kind of method, and in particular to flower-shaped AgPd Nanoalloys and its be catalyzed in the electro-catalysis of formates oxidation reaction and surface plasma
On application.
Background technology
Chemical energy efficiently can be converted to electric energy by fuel liquid battery, have than energy high, fuel transport convenient and
The features such as environmental-friendly, can play huge application potential in the fields such as portable power and electric vehicle.Wherein, with liquid
Formic acid be fuel direct methanoic acid fuel cell due to its high open circuit voltage, hypotoxicity and low fuel permeability, receive people
Growing interest, one of the key factor for influencing direct methanoic acid fuel cell performance is Oxidation of Formic Acid reaction, and in acid medium
Oxidation of Formic Acid reaction compare, the formates oxidation reaction in alkaline medium shows faster kinetics and smaller mistake
Current potential.Moreover, in alkaline medium, the stability of some non-noble metal oxygen reduction electro-catalysts is preferable, further reduces
The totle drilling cost of fuel cell.Therefore, in the past few years, directly alkaline formates fuel cell is always the heat studied
Point.
The catalyst for being catalyzed formates oxidation reaction is mainly precious metals pt and Pd, and the reserves of Pd are more rich, catalytic activity
It is better, so directly the anode catalyst of formates fuel cell is to be commercialized based on Pd/C catalyst.But Pd/C business
Catalyst still has the shortcomings of of high cost, Pd nano particles easy reunion and electrochemical stability is poor, to hinder direct first
The large-scale commercial application of hydrochlorate fuel cell.Currently, the doping of Pd or alloying are the effective ways solved these problems,
Pd-M (M=Ag, Cu, Au) alloy can effectively improve the electrocatalysis characteristic of Pd base catalyst.
Document (Electrochimica Acta 210 (2016) 285) is prepared for a kind of Pd- by technique for atomic layer deposition
On-Ag/CNTs catalyst, as a result, it has been found that its catalytic activity, stability and anti-poisoning capability all significantly improve.
Document (Electrochimica Acta 137 (2014) 654) is prepared for PdCu/C electricity using solution reduction and urges
Agent, catalytic activity and stability are all significantly improved than Pd/C commercial catalysts.
It is reported in document (International Journal of Hydrogen Energy 38 (2013) 15532)
A kind of PdAu core shell nanoparticles have higher catalytic activity, are better than palladium black commercial catalysts.
Document (International Journal of Hydrogen Energy 41 (2016) 13190) uses humidifying
Method has synthesized the CuPdAu/C catalyst that average grain diameter is about 15nm, and catalytic activity and stability are all far above Pd/C business
Catalyst.
Although Pd-M (M=Ag, Cu, Au) Nanoalloys have had first stepping in electro-catalysis formates oxidation reaction
Exhibition, but Pd-M alloying effects are not so good as Oxidation of Formic Acid, and hydrogen reduction and methanol oxidation electrocatalysis characteristic improve notable.Formates
The Pd-M alloying effects of oxidation reaction electrocatalysis characteristic are not notable, and electro catalytic activity is not excellent enough, and cost is excessively high, it is difficult to meet
Current commercial fuel cell such as needs at the problems of the prior art.
Invention content
Technical problems to be solved
In order to avoid the shortcomings of the prior art, a kind of flower-shaped AgPd Nanoalloys of present invention proposition and preparation and use
Method is the preparation method and a kind of surface plasma of a kind of formates oxidation reaction with flower-shaped AgPd nanometer alloy catalysts
The method that resonance technique improves electrocatalysis characteristic.
Technical solution
A kind of flower-shaped AgPd Nanoalloys, it is characterised in that the atomic percent of component is：25~75% silver and 25~
75% palladium；Average grain diameter is 320nm.
The electrochemistry specific surface area of the flower-shaped AgPd Nanoalloys is 3.79~10.37m2/g。
A kind of preparation method of the flower-shaped AgPd Nanoalloys, it is characterised in that steps are as follows：
Step 1：3- Aminopyrazine -2- carboxylic acids (Apzc) are added in distilled water, magnetic agitation is abundant to dissolving；Then to
Palladium salt and silver nitrate (AgNO are added in the Apzc solution that stirred3), magnetic agitation 5min at room temperature；
In the solution：A concentration of 10~60mmol/L of Apzc, palladium salt and AgNO3Total concentration be 4mmol/L, palladium
Salt：AgNO3Substance amount ratio be 1:0~3；
Step 2：1mL ascorbic acid solutions are added, are stirred to react 0.5~2h at room temperature；It is molten to add 0.1mL hydrazine hydrates
Liquid continues to be stirred to react 10~50min；
A concentration of 0.1mol/L of the ascorbic acid solution；
The mass fraction of hydrazine hydrate is 80% in the hydrazine hydrate solution；
Step 3：It is centrifuged at 6000~10000r/min, using distilled water and absolute ethyl alcohol respectively washing 3 times, finally
The product of washes clean is put into freeze drier dry 8~20h, obtains flower-shaped AgPd Nanoalloys.
The palladium salt is that tetrachloro-palladium acid receives Na2PdCl4, chlorine palladium acid H2PdCl4Or palladium nitrate Pd (NO3)2。
The chlorine palladium acid is by palladium bichloride PdCl2Ultrasonic dissolution obtains H in HCl solution2PdCl4。
A concentration of 0.1mol/L of the HCl solution.
A kind of application method of the flower-shaped AgPd Nanoalloys, it is characterised in that：For formates oxidation reaction electricity
In catalysis and surface plasma catalysis.
Advantageous effect
A kind of flower-shaped AgPd Nanoalloys proposed by the present invention and preparation and application are to utilize solution coreduction legal system
A kind of standby flower-shaped PdAg nanometer alloy catalysts, it is alloy element to introduce relatively inexpensive Ag, uses ascorbic acid and hydrazine hydrate
For reducing agent, using Apzc as pattern controlling agent, the average grain diameter for the AgPd nanometer alloy catalysts prepared is 320nm,
Favorable dispersibility, pattern are flower-shaped, and wherein content silver-colored in AgPd nanometer alloy catalysts is 25~75%, and the content of palladium is 25
~75%, the percentage is atomic percent.The electrochemistry specific surface area of flower-shaped AgPd nanometer alloy catalysts is 3.79
~10.37m2/ g, has excellent a catalytic activity and stability, and current density in 0.7V vs.RHE is 1.75~
26.16mA/cm2.Under simulated solar illumination, the pure Pd and Ag that prepare50Pd50The oxidation peak current of nanometer alloy catalyst point
Not from 8.52mA/cm2It is increased to 9.11mA/cm2, and from 26.16mA/cm2It is increased to 30.97mA/cm2。
The flower-shaped AgPd nanometer alloy catalysts of the present invention have excellent catalytic activity and stability, and are simulating too
Under sunlight shines, pure Pd and Ag50Pd50The catalytic activity of nanometer alloy catalyst significantly improves, and concrete outcome is shown in attached drawing 2~6.This
Preparation method and application range to expand formates oxidation reaction catalyst provides certain theories integration and technological guidance.
As shown in Fig. 1, it is that the electro-catalysis of formates oxidation reaction and surface plasma catalysis are received with AgPd in the present invention
The preparation flow of meter He Jin.Attached drawing 2 illustrates cyclic voltammetry curve of the different catalysts in 1M KOH solutions, based in figure
The reduction peak of PdO can obtain, pure Pd, Ag25Pd75、Ag50Pd50And Ag75Pd25Electrochemically active specific surface area be respectively
4.64,3.79,10.37 and 7.8m2/g.Flower-shaped Ag50Pd50 alloy catalysts possess the electrochemically active specific surface area of bigger, say
Bright flower-shaped Ag50Pd50Alloy catalyst has more active site.Attached drawing 3 illustrates different catalysts in 1M KOH+
Cyclic voltammetry curve in 1M KCOOH solution, is compared with attached drawing 2, and after 1M KCOOH are added, Pd base catalyst has one
A apparent formates oxidation peak, and the formates oxidation current of pure Ag catalyst is almost 0.Attached drawing 4 illustrates different catalysis
Polarization current curve of the agent in the case where current potential is 0.425V, it can be seen from the figure that the electric current in starting stage all catalyst is close
The linear downward trend of degree, after a period of time, starts to tend towards stability.After test process, the current density sequence of reservation：
Ag50Pd50> Ag25Pd75The pure Pd > Ag of >75Pd25, pure Pd catalyst is compared, the stability of AgPd nanometer alloy catalysts is all bright
It is aobvious to improve, and Ag50Pd50Alloy catalyst optimal stability.Attached drawing 5 illustrates pure Pd under whether there is or not simulated solar illumination
Cyclic voltammetry curve comparison diagram, it can be seen from the figure that when there is simulated solar illumination, the current potential of formates oxidation peak is negative to be moved,
The electric current of formates oxidation peak is by original 8.52mA/cm2It is increased to 9.11mA/cm2.Attached drawing 6 illustrates flower-shaped Ag50Pd50Alloy
Catalyst is whether there is or not the cyclic voltammetry curves under solar irradiation, it can be seen from the figure that when there is simulated solar illumination, formates
Oxidation peak current is by original 26.16mA/cm2It is increased to 30.97mA/cm2, while the negative shifting of current potential under same current density.
The present invention makees reducing agent using ascorbic acid and hydrazine hydrate, is not related to the use of high toxicity material, and avoids
Use the process of dangerous higher reducibility gas high-temperature calcination.
The present invention is regulated and controled while reducing precious metals pd dosage by pattern control and ingredient, is provided a kind of flower-shaped
The preparation method of AgPd nanometer alloy catalysts.It, can be to the surface of catalyst by controlling the rate of charge of two kinds of metallic precursors
Chemical composition is effectively adjusted.This method is easy to operate, and manufacturing cost is cheap, and repeatability is high, is suitble to large-scale production.
Description of the drawings
Fig. 1：The preparation flow figure of the present invention
Fig. 2：Cyclic voltammetry curve of the different catalysts in 1M KOH solutions；In figure：
Curve 1 is cyclic voltammetry curve of the pure Pd catalyst of the preparation of embodiment 1 in 1M KOH solutions；
Curve 2 is Ag prepared by embodiment 225Pd75Cyclic voltammetric of the nanometer alloy catalyst in 1M KOH solutions is bent
Line；
Curve 3 is Ag prepared by embodiment 350Pd50Cyclic voltammetric of the nanometer alloy catalyst in 1M KOH solutions is bent
Line；
Curve 4 is Ag prepared by embodiment 475Pd25Cyclic voltammetric of the nanometer alloy catalyst in 1M KOH solutions is bent
Line；
Curve 5 is cyclic voltammetry curve of the pure Ag catalyst of the preparation of embodiment 5 in 1M KOH solutions.
Fig. 3：Cyclic voltammetry curve figure of the different catalysts in 1M KOH+1M KCOOH solution；In figure：
Curve 6 is cyclic voltammetry curve of the pure Pd catalyst of the preparation of embodiment 1 in 1M KOH+1M KCOOH solution；
Curve 7 is Ag prepared by embodiment 225Pd75Nanometer alloy catalyst following in 1M KOH+1M KCOOH solution
Ring volt-ampere curve；
Curve 8 is Ag prepared by embodiment 350Pd50Nanometer alloy catalyst following in 1M KOH+1M KCOOH solution
Ring volt-ampere curve；
Curve 9 is Ag prepared by embodiment 475Pd25Nanometer alloy catalyst following in 1M KOH+1M KCOOH solution
Ring volt-ampere curve；
Curve 10 is cyclic voltammetry curve of the pure Ag catalyst of the preparation of embodiment 5 in 1M KOH+1M KCOOH solution.
Fig. 4：Polarization current curve of the different catalysts under 0.425V constant potentials；In figure：
Curve 11 is polarization current curve of the pure Pd catalyst of the preparation of embodiment 1 under 0.425V constant potentials；
Curve 12 is Ag prepared by embodiment 225Pd75Polarization current of the nanometer alloy catalyst under 0.425V constant potentials
Curve；
Curve 13 is Ag prepared by embodiment 350Pd50Polarization current of the nanometer alloy catalyst under 0.425V constant potentials
Curve；
Curve 14 is Ag prepared by embodiment 475Pd25Polarization current of the nanometer alloy catalyst under 0.425V constant potentials
Curve.
Fig. 5：The cyclic voltammetry curve of pure Pd catalyst prepared by embodiment 1 in 1M KOH+1M KCOOH solution；Figure
In：
Curve 15 is the cyclic voltammetry curve under no simulated solar illumination；
Curve 16 is the cyclic voltammetry curve in the case where there is simulated solar illumination.
Fig. 6：Ag prepared by embodiment 350Pd50Cycle volt of the nanometer alloy catalyst in 1M KOH+1M KCOOH solution
Pacify curve graph.
Curve 17 is the cyclic voltammetry curve under no simulated solar illumination；
Curve 18 is the cyclic voltammetry curve in the case where there is simulated solar illumination.
Specific implementation mode
In conjunction with embodiment, attached drawing, the invention will be further described：
Embodiment 1
The present embodiment is a kind of pure Pd catalyst, and the electrochemistry specific surface area of pure Pd catalyst is 4.64m2/ g, in 0.69V
Current density when vs.RHE can reach 8.52mA/cm2.Under simulated solar illumination, the oxidation peak current of pure Pd catalyst from
8.52mA/cm2It is increased to 9.11mA/cm2.The preparation process of the present embodiment is as follows：
(1) it weighs 0.0348g Apzc to be added in 6.9mL distilled water, magnetic agitation is abundant to dissolving.Then to stirring
2mL Na are added in the Apzc solution2PdCl4(20mmol/L), at room temperature magnetic agitation 5min.The concentration of the wherein described Apzc
For 25mmol/L, Na2PdCl4A concentration of 4mmol/L.
(2) 1mL ascorbic acid solutions (0.1mol/L) are rapidly injected into precursor solution obtained by step (1), at room temperature
It is stirred to react 1h.0.1mL hydrazine hydrates (80wt%) are added, continue to be stirred to react 30min.
(3) it centrifuges, is respectively washed 3 times with distilled water and absolute ethyl alcohol, finally by the production of washes clean under 8000r/min
Object is put into freeze drier dry 12h, obtains pure Pd catalyst.
(4) research of the electro-catalysis of formates oxidation reaction and surface plasma catalysis
The pure Pd catalyst on glass-carbon electrode is added dropwise as working electrode, platinum electrode is used as to electrode, mercury/oxidation
Mercury electrode builds three-electrode electrochemical test system as reference electrode.Catalyst is tested in the 1M KOH Jing Guo nitrogen deoxygenation
Cyclic voltammetry curve in solution.It is bent to test catalyst cyclic voltammetric in the 1M KOH+1M KCOOH solution Jing Guo nitrogen deoxygenation
Line.In the 1M KOH+1M KCOOH solution Jing Guo nitrogen deoxygenation, polarization current of the test catalyst under 0.425V constant potentials
Curve.Under simulated solar illumination, catalyst cyclic voltammetric in the 1M KOH+1M KCOOH solution Jing Guo nitrogen deoxygenation is tested
Curve.Potential window is -0.9~0.2V, sweep speed 50mV/s.
Embodiment 2
The present embodiment is a kind of Ag25Pd75Nanometer alloy catalyst, Ag25Pd75Silver-colored content is in nanometer alloy catalyst
26%, the content of palladium is 74%, and the percentage is atomic percent.Ag25Pd75The electrochemistry ratio of nanometer alloy catalyst
Surface area is 3.79m2/ g, the current density in 0.71V vs.RHE are 18.98mA/cm2.The preparation process of the present embodiment is such as
Under：
(1) it weighs 0.0348g Apzc to be added in 6.9mL distilled water, magnetic agitation is abundant to dissolving.Then to stirring
1.5mL Na are added in the Apzc solution2PdCl4(20mmol/L) and 0.5mL AgNO3(20mmol/L), magnetic force stirs at room temperature
Mix 5min.Wherein, a concentration of 25mmol/L, Na of the Apzc2PdCl4A concentration of 3mmol/L, AgNO3It is a concentration of
1mmol/L。
(2) 1mL ascorbic acid solutions (0.1mol/L) are rapidly injected into precursor solution obtained by step (1), at room temperature
It is stirred to react 1h.0.1mL hydrazine hydrates (80wt%) are added, continue to be stirred to react 30min.
(3) it centrifuges, is respectively washed 3 times with distilled water and absolute ethyl alcohol, finally by the production of washes clean under 8000r/min
Object is put into freeze drier and is dried, and obtains AgPd alloy catalysts.Na in the catalyst2PdCl4With AgNO3Substance
The ratio between amount is 3:1, it is denoted as Ag25Pd75。
(4) research of formates oxidation reaction electro-catalysis
The Ag on glass-carbon electrode is added dropwise25Pd75Nanometer alloy catalyst is as working electrode, platinum electrode conduct pair
Electrode, mercury/mercuric oxide electrode build three-electrode electrochemical test system as reference electrode.Catalyst is tested by nitrogen
Cyclic voltammetry curve in the 1M KOH solutions of deoxygenation.Catalyst is tested in the 1M KOH+1M KCOOH solution Jing Guo nitrogen deoxygenation
Middle cyclic voltammetry curve.In the 1M KOH+1M KCOOH solution Jing Guo nitrogen deoxygenation, test catalyst is in 0.425V constant potentials
Under polarization current curve.Potential window is -0.9~0.2V, sweep speed 50mV/s.
Embodiment 3
The present embodiment is a kind of Ag50Pd50Nanometer alloy catalyst, Ag50Pd50The average grain diameter of nanometer alloy catalyst is
320nm, favorable dispersibility, pattern are flower-shaped, Ag50Pd50Silver-colored content is 51% in nanometer alloy catalyst, and the content of palladium is
49%, the percentage is atomic percent.Ag25Pd75The electrochemistry specific surface area of nanometer alloy catalyst is 10.37m2/
G, the current density in 0.74V vs.RHE are 26.16mA/cm2.Under simulated solar illumination, Ag50Pd50Nanoalloy is catalyzed
The oxidation peak current of agent is from 26.16mA/cm2It is increased to 30.97mA/cm2.The preparation process of the present embodiment is as follows：
(1) it weighs 0.0348g Apzc to be added in 6.9mL distilled water, magnetic agitation is abundant to dissolving.Then to stirring
It is separately added into 1mL Na in the Apzc solution2PdCl4(20mmol/L) and 1mL AgNO3(20mmol/L), magnetic force stirs at room temperature
Mix 5min.Wherein, a concentration of 25mmol/L, Na of the Apzc2PdCl4A concentration of 2mmol/L, AgNO3It is a concentration of
2mmol/L。
(2) 1mL ascorbic acid solutions (0.1mol/L) are rapidly injected into precursor solution obtained by step (1), at room temperature
It is stirred to react 1h.0.1mL hydrazine hydrates (80wt%) are added, continue to be stirred to react 30min.
(3) it centrifuges, is respectively washed 3 times with distilled water and absolute ethyl alcohol, finally by the production of washes clean under 8000r/min
Object is put into freeze drier dry 12h, obtains flower-shaped AgPd alloy catalysts.Na in the catalyst2PdCl4With AgNO3Substance
The ratio between amount be 1:1, it is denoted as Ag50Pd50。
(4) research of the electro-catalysis of formates oxidation reaction and surface plasma catalysis
The Ag on glass-carbon electrode is added dropwise50Pd50Nanometer alloy catalyst is as working electrode, platinum electrode conduct pair
Electrode, mercury/mercuric oxide electrode build three-electrode electrochemical test system as reference electrode.Catalyst is tested by nitrogen
Cyclic voltammetry curve in the 1M KOH solutions of deoxygenation.Catalyst is tested in the 1M KOH+1M KCOOH solution Jing Guo nitrogen deoxygenation
Middle cyclic voltammetry curve.In the 1M KOH+1M KCOOH solution Jing Guo nitrogen deoxygenation, test catalyst is in 0.425V constant potentials
Under polarization current curve.Under simulated solar illumination, test catalyst is molten in the 1M KOH+1M KCOOH Jing Guo nitrogen deoxygenation
Cyclic voltammetry curve in liquid.Potential window is -0.9~0.2V, sweep speed 50mV/s.
Embodiment 4
The present embodiment is a kind of Ag75Pd25Nanometer alloy catalyst, Ag75Pd25Silver-colored content is in nanometer alloy catalyst
74%, the content of palladium is 26%, and the percentage is atomic percent.Ag75Pd25The electrochemistry ratio of nanometer alloy catalyst
Surface area is 7.85m2/ g, the current density in 0.6V vs.RHE are 1.75mA/cm2.The preparation process of the present embodiment is as follows：
(1) it weighs 0.0348g Apzc to be added in 6.9mL distilled water, magnetic agitation is abundant to dissolving.Then to stirring
It is separately added into 0.5mL Na in the Apzc solution2PdCl4(20mmol/L) and 1.5mL AgNO3(20mmol/L), at room temperature magnetic
Power stirs 5min.Wherein, a concentration of 25mmol/L, Na of the Apzc2PdCl4A concentration of 1mmol/L, AgNO3It is a concentration of
3mmol/L。
(2) 1mL ascorbic acid solutions (0.1mol/L) are rapidly injected into precursor solution obtained by step (1), at room temperature
It is stirred to react 1h.0.1mL hydrazine hydrates (80wt%) are added, continue to be stirred to react 30min.
(3) it centrifuges, is respectively washed 3 times with distilled water and absolute ethyl alcohol, finally by the production of washes clean under 8000r/min
Object is put into freeze drier dry 12h, obtains flower-shaped AgPd alloy catalysts.Na in the catalyst2PdCl4With AgNO3Substance
The ratio between amount be 1:3, it is denoted as Ag75Pd25。
(4) research of formates oxidation reaction electro-catalysis
The Ag on glass-carbon electrode is added dropwise75Pd25Nanometer alloy catalyst is as working electrode, platinum electrode conduct pair
Electrode, mercury/mercuric oxide electrode build three-electrode electrochemical test system as reference electrode.Catalyst is tested by nitrogen
Cyclic voltammetry curve in the 1M KOH solutions of deoxygenation.Catalyst is tested in the 1M KOH+1M KCOOH solution Jing Guo nitrogen deoxygenation
Middle cyclic voltammetry curve.In the 1M KOH+1M KCOOH solution Jing Guo nitrogen deoxygenation, test catalyst is in 0.425V constant potentials
Under polarization current curve.Potential window is -0.9~0.2V, sweep speed 50mV/s.
Embodiment 5
The present embodiment is a kind of pure Ag catalyst, and the oxidation peak current of pure Ag catalyst only has 0.28mA/cm2, can neglect
Slightly disregard.The preparation process of the present embodiment is as follows：
(1) it weighs 0.0348g Apzc to be added in 6.9mL distilled water, magnetic agitation is abundant to dissolving.Then to stirring
2mL AgNO are added in the Apzc solution3(20mmol/L), at room temperature magnetic agitation 5min.Wherein, the concentration of the Apzc
For 25mmol/L, AgNO3A concentration of 4mmol/L.
(2) 1mL ascorbic acid solutions (0.1mol/L) are rapidly injected into precursor solution obtained by step (1), at room temperature
It is stirred to react 1h.0.1mL hydrazine hydrates (80wt%) are added, continue to be stirred to react 30min.
(3) it centrifuges, is respectively washed 3 times with distilled water and absolute ethyl alcohol, finally by the production of washes clean under 8000r/min
Object is put into freeze drier dry 12h, obtains pure Ag catalyst.
(4) research of formates oxidation reaction electro-catalysis
The pure Ag catalyst on glass-carbon electrode is added dropwise as working electrode, platinum electrode is used as to electrode, mercury/oxidation
Mercury electrode builds three-electrode electrochemical test system as reference electrode.Catalyst is tested in the 1M KOH Jing Guo nitrogen deoxygenation
Cyclic voltammetry curve in solution.It is bent to test catalyst cyclic voltammetric in the 1M KOH+1M KCOOH solution Jing Guo nitrogen deoxygenation
Line.Potential window is -0.9~0.2V, sweep speed 50mV/s.
Embodiment 6
The present embodiment is a kind of Ag50Pd50Nanometer alloy catalyst, the catalyst of preparation can effectively be catalyzed the oxygen of formates
Change, the peak current provided at 0.74V is 20.8mA/cm2.The preparation process of the present embodiment is as follows：
(1) it weighs 0.0348g Apzc to be added in 6.9mL distilled water, magnetic agitation is abundant to dissolving.Then to stirring
1mL H are added in the Apzc solution2PdCl4(20mmol/L) and 1mL AgNO3(20mmol/L), at room temperature magnetic agitation
5min.Wherein, a concentration of 25mmol/L, H of the Apzc2PdCl4A concentration of 2mmol/L, AgNO3A concentration of 2mmol/
L。
(2) 1mL ascorbic acid solutions (0.1mol/L) are rapidly injected into precursor solution obtained by step (1), at room temperature
It is stirred to react 1h.0.1mL hydrazine hydrates (80wt%) are added, continue to be stirred to react 30min.
(3) it centrifuges, is respectively washed 3 times with distilled water and absolute ethyl alcohol, finally by the production of washes clean under 8000r/min
Object is put into freeze drier dry 12h, obtains flower-shaped AgPd alloy catalysts.H in the catalyst2PdCl4With AgNO3Substance
The ratio between amount be 1:1, it is denoted as Ag50Pd50。
(4) research of formates oxidation reaction electro-catalysis
The Ag on glass-carbon electrode is added dropwise50Pd50As working electrode, platinum electrode is used as to electrode alloy catalyst,
Mercury/mercuric oxide electrode builds three-electrode electrochemical test system as reference electrode.Catalyst is tested by nitrogen deoxygenation
Cyclic voltammetry curve in 1M KOH solutions.Test catalyst recycles in the 1M KOH+1M KCOOH solution Jing Guo nitrogen deoxygenation
Volt-ampere curve.Potential window is -0.9~0.2V, sweep speed 50mV/s.
Embodiment 7
The present embodiment is a kind of Ag50Pd50The catalyst of nanometer alloy catalyst, preparation can effectively be catalyzed formates
Oxidation, the peak current density provided at 0.75V are 25.2mA/cm2.The preparation process of the present embodiment is as follows：
(1) it weighs 0.0348g Apzc to be added in 6.9mL distilled water, magnetic agitation is abundant to dissolving.Then to stirring
1mL Pd (NO are separately added into the Apzc solution3)2(20mmol/L) and 1mL AgNO3(20mmol/L), magnetic force stirs at room temperature
Mix 5min.Wherein, a concentration of 25mmol/L of the Apzc, Pd (NO3)2A concentration of 2mmol/L, AgNO3It is a concentration of
2mmol/L。
(2) 1mL ascorbic acid solutions (0.1mol/L) are rapidly injected into precursor solution obtained by step (1), at room temperature
It is stirred to react 1h.0.1mL hydrazine hydrates (80wt%) are added, continue to be stirred to react 30min.
(3) it centrifuges, is respectively washed 3 times with distilled water and absolute ethyl alcohol, finally by the production of washes clean under 8000r/min
Object is put into freeze drier dry 12h, obtains AgPd nanometer alloy catalysts.Pd (NO in the catalyst3)2With AgNO3Substance
The ratio between amount be 1:1, it is denoted as Ag50Pd50。
(4) research of formates oxidation reaction electro-catalysis
The Ag on glass-carbon electrode is added dropwise50Pd50Nanometer alloy catalyst is as working electrode, platinum electrode conduct pair
Electrode, mercury/mercuric oxide electrode build three-electrode electrochemical test system as reference electrode.Catalyst is tested by nitrogen
Cyclic voltammetry curve in the 1M KOH solutions of deoxygenation.Catalyst is tested in the 1M KOH+1M KCOOH solution Jing Guo nitrogen deoxygenation
Middle cyclic voltammetry curve.Potential window is -0.9~0.2V, sweep speed 50mV/s.
Claims (7)
1. a kind of flower-shaped AgPd Nanoalloys, it is characterised in that the atomic percent of component is：25~75% silver and 25~
75% palladium；Average grain diameter is 320nm.
2. flower-shaped AgPd Nanoalloys according to claim 1, it is characterised in that：The electrification of the flower-shaped AgPd Nanoalloys
Specific surface area is 3.79~10.37m2/g。
3. the preparation method of flower-shaped AgPd Nanoalloys described in a kind of claims 1 or 2, it is characterised in that steps are as follows：
Step 1：3- Aminopyrazine -2- carboxylic acids (Apzc) are added in distilled water, magnetic agitation is abundant to dissolving；Then to stirring
Palladium salt and silver nitrate (AgNO are added in the Apzc solution3), magnetic agitation 5min at room temperature；
In the solution：A concentration of 10~60mmol/L of Apzc, palladium salt and AgNO3Total concentration be 4mmol/L, palladium salt：
AgNO3Substance amount ratio be 1:0~3；
Step 2：1mL ascorbic acid solutions are added, are stirred to react 0.5~2h at room temperature；0.1mL hydrazine hydrate solutions are added,
Continue to be stirred to react 10~50min；
A concentration of 0.1mol/L of the ascorbic acid solution；
The mass fraction of hydrazine hydrate is 80% in the hydrazine hydrate solution；
Step 3：It centrifuges at 6000~10000r/min, using distilled water and absolute ethyl alcohol respectively washing 3 times, will finally wash
It washs clean product and is put into freeze drier dry 8~20h, obtain flower-shaped AgPd Nanoalloys.
4. according to the method described in claim 3, it is characterized in that：The palladium salt is that tetrachloro-palladium acid receives Na2PdCl4, chlorine palladium acid
H2PdCl4Or palladium nitrate Pd (NO3)2。
5. according to the method described in claim 4, it is characterized in that：The chlorine palladium acid is by palladium bichloride PdCl2Ultrasonic dissolution in
HCl solution obtains H2PdCl4。
6. according to the method described in claim 5, it is characterized in that：A concentration of 0.1mol/L of the HCl solution.
7. a kind of application method of flower-shaped AgPd Nanoalloys described in claim 1, it is characterised in that：It is aoxidized for formates
It reacts in electro-catalysis and surface plasma catalysis.
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