CN108746659B - Flower-shaped AgPd nano alloy and preparation and use methods thereof - Google Patents
Flower-shaped AgPd nano alloy and preparation and use methods thereof Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 96
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 36
- 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
- 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 16
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 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
- 229910052709 silver Inorganic materials 0.000 claims abstract description 12
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
- 239000004332 silver Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 45
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 22
- 239000012153 distilled water Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000006555 catalytic reaction Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 150000002940 palladium Chemical class 0.000 claims description 8
- 229910003603 H2PdCl4 Inorganic materials 0.000 claims description 6
- 101710134784 Agnoprotein Proteins 0.000 claims description 5
- ZAGZIOYVEIDDJA-UHFFFAOYSA-N 3-aminopyrazine-2-carboxylic acid Chemical compound NC1=NC=CN=C1C(O)=O ZAGZIOYVEIDDJA-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 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
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical group [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 118
- 238000005286 illumination Methods 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000005275 alloying Methods 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 229910021124 PdAg Inorganic materials 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 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 38
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 12
- 239000000446 fuel Substances 0.000 description 11
- 230000010287 polarization Effects 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 238000000840 electrochemical analysis Methods 0.000 description 7
- 229910021397 glassy carbon Inorganic materials 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- 229910000474 mercury oxide Inorganic materials 0.000 description 7
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 7
- 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 6
- 235000019253 formic acid Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
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- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
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- 229910052760 oxygen 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
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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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
-
- 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
-
- B01J35/33—
-
- B01J35/40—
-
- B01J35/50—
-
- 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
- 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
-
- 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
- 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
- B22F1/0553—Complex form nanoparticles, e.g. prism, pyramid, octahedron
-
- 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
Abstract
The invention relates to a flower-shaped AgPd nano alloy and a preparation and use method thereof, wherein a solution co-reduction method is utilized to prepare a flower-shaped PdAg nano alloy catalyst, cheap Ag is introduced as an alloying element, ascorbic acid and hydrazine hydrate are used as reducing agents, Apzc is used as a morphology control agent, and the average particle size of the prepared AgPd nano alloy catalyst is 320nm, the dispersity is good, and the morphology is flower-shaped, wherein the content of silver in the AgPd nano alloy catalyst is 25-75%, the content of palladium in the AgPd nano alloy catalyst is 25-75%, and the percentages are atomic percentages. The electrochemical specific surface area of the flower-shaped AgPd nano-alloy catalyst is 3.79-10.37 m2The catalyst has excellent catalytic activity and stability, and the current density at 0.7V vs. RHE is 1.75-26.16 mA/cm2. Pure Pd and Ag prepared under simulated solar illumination50Pd50The oxidation peak current of the nano alloy catalyst is respectively from 8.52mA/cm2Increased to 9.11mA/cm2And from 26.16mA/cm2Increased to 30.97mA/cm2。
Description
Technical Field
The invention belongs to the technical field of electro-catalysis and photocatalysis, relates to a flower-shaped AgPd nano alloy and preparation and use methods thereof, and particularly relates to a flower-shaped AgPd nano alloy and application thereof in formate oxidation reaction electro-catalysis and surface plasma catalysis.
Background
The liquid fuel cell can efficiently convert chemical energy into electric energy, has the characteristics of high specific energy, convenient fuel transportation, environmental friendliness and the like, and can play a great application potential in the fields of portable power supplies, electric automobiles and the like. Among them, the direct formic acid fuel cell using liquid formic acid as fuel is receiving increasing attention due to its high open circuit voltage, low toxicity and low fuel permeability, one of the key factors affecting the performance of the direct formic acid fuel cell is formic acid oxidation reaction, and compared with formic acid oxidation reaction in acidic medium, formate oxidation reaction in alkaline medium shows faster reaction kinetics and smaller overpotential. Moreover, some non-noble metal oxygen-reducing electrocatalysts are more stable in alkaline media, further reducing the overall cost of the fuel cell. Thus, over the past few years, direct alkaline formate fuel cells have been the focus of research.
The catalyst for catalyzing the formate oxidation reaction is mainly noble metals of Pt and Pd, the reserves of Pd are more abundant, and the catalytic activity is more excellent, so that the anode catalyst of the direct formate fuel cell is mainly a commercial Pd/C catalyst. However, the commercial Pd/C catalyst still has the disadvantages of high cost, easy agglomeration of Pd nanoparticles, poor electrochemical stability and the like, thereby preventing the large-scale commercial application of the direct formate fuel cell. Currently, doping or alloying of Pd is an effective method to solve these problems, and Pd — M (M ═ Ag, Cu, Au) alloys can effectively improve the electrocatalytic performance of Pd-based catalysts.
The document (Electrochimica Acta 210(2016)285) prepares a Pd-on-Ag/CNTs catalyst by an atomic layer deposition technology, and the result shows that the catalytic activity, the stability and the anti-poisoning capability of the Pd-on-Ag/CNTs catalyst are obviously improved.
The document (Electrochimica Acta 137(2014)654) prepares the PdCu/C electrocatalyst by a solution reduction method, and the catalytic activity and the stability of the PdCu/C electrocatalyst are obviously improved compared with those of a Pd/C commercial catalyst.
A PdAu core-shell nanoparticle reported in the literature (International Journal of Hydrogen Energy 38(2013)15532) has higher catalytic activity and is superior to a palladium black commercial catalyst.
The literature (International Journal of Hydrogen Energy 41(2016)13190) synthesizes CuPdAu/C catalyst with average particle size of about 15nm by wet chemical method, and the catalytic activity and stability of the CuPdAu/C catalyst are far higher than those of Pd/C commercial catalyst.
Although the Pd-M (M ═ Ag, Cu and Au) nano alloy has been developed primarily in the electrocatalytic formate oxidation reaction, the Pd-M alloying effect is not as good as that of formic acid oxidation, and the electrocatalytic performance of oxygen reduction and methanol oxidation reactions is improved obviously. The Pd-M alloying effect of the electro-catalytic performance of formate oxidation reaction is not obvious, the electro-catalytic activity is not good enough, the cost is too high, the current requirements of commercial fuel cells are difficult to meet, and the like.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a flower-shaped AgPd nano alloy and a preparation and use method thereof, and discloses a preparation method of a flower-shaped AgPd nano alloy catalyst for formate oxidation reaction and a method for improving electrocatalysis performance by using a surface plasma resonance technology.
Technical scheme
A flower-shaped AgPd nano alloy is characterized by comprising the following components in percentage by atom: 25-75% of silver and 25-75% of palladium; the average particle size was 320 nm.
The electrochemical specific surface area of the flower-shaped AgPd nano alloy is 3.79-10.37 m2/g。
A preparation method of the flower-shaped AgPd nano alloy is characterized by comprising the following steps:
step 1: adding 3-aminopyrazine-2-carboxylic acid (Apzc) into distilled water, and magnetically stirring until the solution is fully dissolved; palladium salt and silver nitrate (AgNO) are then added to the stirred Apzc solution3) Magnetically stirring at room temperature for 5 min;
in the solution: the concentration of Apzc is 10-60 mmol/L, and the palladium salt and AgNO are34mmol/L, palladium salt: AgNO3The amount ratio of the substances (A) to (B) is 1: 0-3;
step 2: then adding 1mL of ascorbic acid solution, and stirring and reacting for 0.5-2 h at room temperature; then adding 0.1mL of hydrazine hydrate solution, and continuously stirring for reaction for 10-50 min;
the concentration of the ascorbic acid solution is 0.1 mol/L;
the mass fraction of hydrazine hydrate in the hydrazine hydrate solution is 80 percent;
and step 3: and (3) performing centrifugal separation at 6000-10000 r/min, washing for 3 times by using distilled water and absolute ethyl alcohol respectively, and finally drying the washed product in a freeze dryer for 8-20 hours to obtain the flower-shaped AgPd nano alloy.
The palladium salt is sodium tetrachloropalladate Na2PdCl4Chloropalladate H2PdCl4Or palladium nitrate Pd (NO3)2。
The palladium chloride acid is PdCl2Ultrasonic dissolving in HCl solution to obtain H2PdCl4。
The concentration of the HCl solution is 0.1 mol/L.
The use method of the flower-shaped AgPd nano alloy is characterized by comprising the following steps: used for the electrocatalysis of formate oxidation reaction and the surface plasma catalysis.
Advantageous effects
The invention provides a flower-shaped AgPd nano alloy and a preparation and use method thereof, wherein a solution co-reduction method is utilized to prepare a flower-shaped PdAg nano alloy catalyst, cheap Ag is introduced as an alloying element, ascorbic acid and hydrazine hydrate are used as reducing agents, Apzc is used as a morphology control agent, the average particle size of the prepared AgPd nano alloy catalyst is 320nm, the dispersity is good, the morphology is flower-shaped, the content of silver in the AgPd nano alloy catalyst is 25-75%, the content of palladium in the AgPd nano alloy catalyst is 25-75%, and the percentages are atomic percentages. The electrochemical specific surface area of the flower-shaped AgPd nano-alloy catalyst is 3.79-10.37 m2The catalyst has excellent catalytic activity and stability, and the current density at 0.7V vs. RHE is 1.75-26.16 mA/cm2. Pure Pd and Ag prepared under simulated solar illumination50Pd50The oxidation peak current of the nano alloy catalyst is respectively from 8.52mA/cm2Increased to 9.11mA/cm2And from 26.16mA/cm2Increased to 30.97mA/cm2。
The flower-like AgPd nano-alloy catalyst has excellent catalytic activity and stability, and pure Pd and Ag under simulated solar illumination50Pd50The catalytic activity of the nano alloy catalyst is obviously improved, and specific results are shown in the attached figures 2-6. Therefore, certain theoretical support and technical guidance are provided for expanding the preparation method and the application range of the formate oxidation reaction catalyst.
As shown in attached figure 1, the invention is a preparation process of AgPd nano alloy for formate oxidation reaction electrocatalysis and surface plasma catalysis. FIG. 2 shows cyclic voltammograms of different catalysts in 1M KOH solution, which are obtained based on the reduction peak of PdO in the figure, pure Pd and Ag25Pd75、Ag50Pd50And Ag75Pd25Respectively, the electrochemically active specific surface areas of (a) and (b) are 4.64. 3.79, 10.37 and 7.8m2(ii) in terms of/g. Flower shaped Ag50The Pd50 alloy catalyst has larger electrochemical activity specific surface area, which indicates flower-shaped Ag50Pd50The alloy catalyst has more catalytic active sites. FIG. 3 shows cyclic voltammograms of different catalysts in 1M KOH +1M KCOOH solution, and compared with FIG. 2, the Pd-based catalysts all had a distinct formate oxidation peak after addition of 1M KCOOH, whereas the formate oxidation current of the pure Ag catalyst was almost 0. FIG. 4 shows the polarization current curves of different catalysts at a potential of 0.425V, from which it can be seen that the current densities of all catalysts show a linear decreasing trend in the initial phase and begin to stabilize after a while. After the test procedure was completed, the current density order retained: ag50Pd50＞Ag25Pd75Pure Pd > Ag75Pd25Compared with pure Pd catalyst, the stability of AgPd nano alloy catalyst is obviously improved, and Ag50Pd50The stability of the alloy catalyst is optimal. FIG. 5 shows a comparison graph of cyclic voltammetry curves of pure Pd under the simulated sunlight irradiation, and it can be seen from the graph that, under the simulated sunlight irradiation, the potential of the formate oxidation peak is shifted negatively, and the current of the formate oxidation peak is changed from the original 8.52mA/cm2Increased to 9.11mA/cm2. FIG. 6 shows flower-like Ag50Pd50The cyclic voltammetry curve of the alloy catalyst under the condition of no sunlight illumination can be seen from the figure, and the formate oxidation peak current is changed from the original 26.16mA/cm under the condition of simulated sunlight illumination2Increased to 30.97mA/cm2While at the same time the potential shifts negatively at the same current density.
The invention uses ascorbic acid and hydrazine hydrate as reducing agents, does not relate to the use of high-toxicity materials, and avoids the process of high-temperature calcination by using reducing gas with higher danger.
The invention provides a preparation method of a flower-shaped AgPd nano alloy catalyst by controlling the shape and components while reducing the dosage of noble metal Pd. By controlling the feed ratio of the two metal precursors, the surface chemical composition of the catalyst can be effectively adjusted. The method is simple to operate, low in preparation cost, high in repeatability and suitable for large-scale production.
Drawings
FIG. 1: preparation flow chart of the invention
FIG. 2: cyclic voltammograms of different catalysts in 1M KOH solution; in the figure:
FIG. 3: cyclic voltammograms of different catalysts in 1M KOH +1M KCOOH solution; in the figure:
curve 7 is the Ag prepared in example 225Pd75Cyclic voltammetry of the nano-alloy catalyst in a 1M KOH +1M KCOOH solution;
curve 9 is the Ag prepared in example 475Pd25Cyclic voltammetry of the nano-alloy catalyst in a 1M KOH +1M KCOOH solution;
FIG. 4: polarization current curves of different catalysts at a constant potential of 0.425V; in the figure:
FIG. 5: cyclic voltammogram of the pure Pd catalyst prepared in example 1 in 1M KOH +1M KCOOH solution; in the figure:
FIG. 6: ag prepared in example 350Pd50Cyclic voltammogram of the nanoalloy catalyst in 1M KOH +1M KCOOH solution.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
example 1
This example is a pure Pd catalyst having an electrochemical specific surface area of 4.64m2The current density at 0.69V vs. RHE can reach 8.52mA/cm2. Under simulated solar illumination, the oxidation peak current of the pure Pd catalyst is from 8.52mA/cm2Increased to 9.11mA/cm2. The preparation process of this example is as follows:
(1) 0.0348g of Apzc was weighed into 6.9mL of distilled water and stirred magnetically until dissolved sufficiently. Then 2mL Na was added to the stirred Apzc solution2PdCl4(20mmol/L), and stirred magnetically at room temperature for 5 min. Wherein saidThe concentration of Apzc is 25mmol/L, Na2PdCl4The concentration of (2) was 4 mmol/L.
(2) And (2) quickly injecting 1mL of ascorbic acid solution (0.1mol/L) into the precursor solution obtained in the step (1), and stirring and reacting for 1h at room temperature. Then, 0.1mL of hydrazine hydrate (80 wt%) was added, and the reaction was continued with stirring for 30 min.
(3) Centrifuging at 8000r/min, washing with distilled water and anhydrous ethanol for 3 times, and drying in a freeze drier for 12 hr to obtain pure Pd catalyst.
(4) Research on electro-catalysis and surface plasma catalysis of formate oxidation reaction
A three-electrode electrochemical test system is constructed by taking a pure Pd catalyst dripped on a glassy carbon electrode as a working electrode, a platinum wire electrode as a counter electrode and a mercury/mercury oxide electrode as a reference electrode. The catalysts were tested for cyclic voltammograms in a 1M KOH solution deoxygenated with nitrogen. The catalysts were tested for cyclic voltammograms in a 1M KOH +1M KCOOH solution deoxygenated with nitrogen. The catalyst was tested for polarization current curve at 0.425V constant potential in a 1M KOH +1M KCOOH solution deoxygenated with nitrogen. The catalyst was tested for cyclic voltammograms in a 1M KOH +1M KCOOH solution deoxygenated with nitrogen under simulated solar illumination. The potential window is-0.9-0.2V, and the scanning speed is 50 mV/s.
Example 2
This example is Ag25Pd75Nano alloy catalyst, Ag25Pd75The content of silver in the nano alloy catalyst is 26%, the content of palladium is 74%, and the percentages are atom percentages. Ag25Pd75The electrochemical specific surface area of the nano alloy catalyst is 3.79m2(ii)/g, current density at 0.71V vs. RHE of 18.98mA/cm2. The preparation process of this example is as follows:
(1) 0.0348g of Apzc was weighed into 6.9mL of distilled water and stirred magnetically until dissolved sufficiently. Then 1.5mL Na was added to the stirred Apzc solution2PdCl4(20mmol/L) and 0.5mL AgNO3(20mmol/L), and stirred magnetically at room temperature for 5 min. Wherein the concentration of Apzc is 25mmol/L, Na2PdCl4Has a concentration of 3mmol/L, AgNO3The concentration of (2) was 1 mmol/L.
(2) And (2) quickly injecting 1mL of ascorbic acid solution (0.1mol/L) into the precursor solution obtained in the step (1), and stirring and reacting for 1h at room temperature. Then, 0.1mL of hydrazine hydrate (80 wt%) was added, and the reaction was continued with stirring for 30 min.
(3) And (3) performing centrifugal separation at 8000r/min, washing with distilled water and absolute ethyl alcohol for 3 times respectively, and finally drying the washed product in a freeze dryer to obtain the AgPd alloy catalyst. In the catalyst Na2PdCl4With AgNO3The ratio of the amount of the substance is 3:1 and is marked as Ag25Pd75。
(4) Study on electrocatalysis of formate oxidation reaction
By dropping Ag on glassy carbon electrode25Pd75The nano alloy catalyst is used as a working electrode, the platinum wire electrode is used as a counter electrode, and the mercury/mercury oxide electrode is used as a reference electrode, so that a three-electrode electrochemical test system is constructed. The catalysts were tested for cyclic voltammograms in a 1M KOH solution deoxygenated with nitrogen. The catalysts were tested for cyclic voltammograms in a 1M KOH +1M KCOOH solution deoxygenated with nitrogen. The catalyst was tested for polarization current curve at 0.425V constant potential in a 1M KOH +1M KCOOH solution deoxygenated with nitrogen. The potential window is-0.9-0.2V, and the scanning speed is 50 mV/s.
Example 3
This example is Ag50Pd50Nano alloy catalyst, Ag50Pd50The average grain diameter of the nano alloy catalyst is 320nm, the dispersibility is good, the appearance is flower-shaped, and Ag50Pd50The content of silver in the nano alloy catalyst is 51 percent, the content of palladium in the nano alloy catalyst is 49 percent, and the percentages are atom percentages. Ag25Pd75The electrochemical specific surface area of the nano alloy catalyst is 10.37m2Current density at 0.74V vs. RHE of 26.16mA/cm2. Under simulated solar illumination, Ag50Pd50The oxidation peak current of the nano alloy catalyst is from 26.16mA/cm2Increased to 30.97mA/cm2. The preparation process of this example is as follows:
(1) 0.0348g of Apzc was weighed into 6.9mL of distilled water and stirred magnetically until dissolved sufficiently. Then, 1mL of Na was added to each of the stirred Apzc solutions2PdCl4(20mmol/L) and 1mL AgNO3(20mmol/L), and stirred magnetically at room temperature for 5 min. Wherein the concentration of Apzc is 25mmol/L, Na2PdCl4Has a concentration of 2mmol/L, AgNO3The concentration of (2) was 2 mmol/L.
(2) And (2) quickly injecting 1mL of ascorbic acid solution (0.1mol/L) into the precursor solution obtained in the step (1), and stirring and reacting for 1h at room temperature. Then, 0.1mL of hydrazine hydrate (80 wt%) was added, and the reaction was continued with stirring for 30 min.
(3) Centrifuging at 8000r/min, washing with distilled water and anhydrous ethanol for 3 times, and drying in a freeze drier for 12 hr to obtain flower-shaped AgPd alloy catalyst. In the catalyst Na2PdCl4With AgNO3The ratio of the amount of the substance is 1:1 and is marked as Ag50Pd50。
(4) Research on electro-catalysis and surface plasma catalysis of formate oxidation reaction
By dropping Ag on glassy carbon electrode50Pd50The nano alloy catalyst is used as a working electrode, the platinum wire electrode is used as a counter electrode, and the mercury/mercury oxide electrode is used as a reference electrode, so that a three-electrode electrochemical test system is constructed. The catalysts were tested for cyclic voltammograms in a 1M KOH solution deoxygenated with nitrogen. The catalysts were tested for cyclic voltammograms in a 1M KOH +1M KCOOH solution deoxygenated with nitrogen. The catalyst was tested for polarization current curve at 0.425V constant potential in a 1M KOH +1M KCOOH solution deoxygenated with nitrogen. The catalyst was tested for cyclic voltammograms in a 1M KOH +1M KCOOH solution deoxygenated with nitrogen under simulated solar illumination. The potential window is-0.9-0.2V, and the scanning speed is 50 mV/s.
Example 4
This example is Ag75Pd25Nano alloy catalyst, Ag75Pd25The content of silver in the nano alloy catalyst is 74%, the content of palladium is 26%, and the percentages are atom percentages. Ag75Pd25The electrochemical specific surface area of the nano alloy catalyst is 7.85m2Current density at 0.6V vs. RHE of 1.75mA/cm2. The preparation process of this example is as follows:
(1) 0.0348g of Apzc was weighed into 6.9mL of distilled water and stirred magnetically until dissolved sufficiently. Then, 0.5mL of Na was added to each of the stirred Apzc solutions2PdCl4(20mmol/L) and 1.5mL AgNO3(20mmol/L), and stirred magnetically at room temperature for 5 min. Wherein the concentration of Apzc is 25mmol/L, Na2PdCl4In a concentration of 1mmol/L, AgNO3The concentration of (2) was 3 mmol/L.
(2) And (2) quickly injecting 1mL of ascorbic acid solution (0.1mol/L) into the precursor solution obtained in the step (1), and stirring and reacting for 1h at room temperature. Then, 0.1mL of hydrazine hydrate (80 wt%) was added, and the reaction was continued with stirring for 30 min.
(3) Centrifuging at 8000r/min, washing with distilled water and anhydrous ethanol for 3 times, and drying in a freeze drier for 12 hr to obtain flower-shaped AgPd alloy catalyst. In the catalyst Na2PdCl4With AgNO3The ratio of the amount of the substance is 1:3, and the mark is Ag75Pd25。
(4) Study on electrocatalysis of formate oxidation reaction
By dropping Ag on glassy carbon electrode75Pd25The nano alloy catalyst is used as a working electrode, the platinum wire electrode is used as a counter electrode, and the mercury/mercury oxide electrode is used as a reference electrode, so that a three-electrode electrochemical test system is constructed. The catalysts were tested for cyclic voltammograms in a 1M KOH solution deoxygenated with nitrogen. The catalysts were tested for cyclic voltammograms in a 1M KOH +1M KCOOH solution deoxygenated with nitrogen. The catalyst was tested for polarization current curve at 0.425V constant potential in a 1M KOH +1M KCOOH solution deoxygenated with nitrogen. The potential window is-0.9-0.2V, and the scanning speed is 50 mV/s.
Example 5
This example is a pure Ag catalyst with an oxidation peak current of only 0.28mA/cm2It can be ignored. The preparation process of this example is as follows:
(1) weighing0.0348g of Apzc was added to 6.9mL of distilled water and stirred magnetically until the solution was well dissolved. Then 2mL of AgNO was added to the stirred Apzc solution3(20mmol/L), and stirred magnetically at room temperature for 5 min. Wherein the concentration of Apzc is 25mmol/L, AgNO3The concentration of (2) was 4 mmol/L.
(2) And (2) quickly injecting 1mL of ascorbic acid solution (0.1mol/L) into the precursor solution obtained in the step (1), and stirring and reacting for 1h at room temperature. Then, 0.1mL of hydrazine hydrate (80 wt%) was added, and the reaction was continued with stirring for 30 min.
(3) Centrifuging at 8000r/min, washing with distilled water and anhydrous ethanol for 3 times, and drying in a freeze drier for 12 hr to obtain pure Ag catalyst.
(4) Study on electrocatalysis of formate oxidation reaction
A three-electrode electrochemical test system is constructed by taking a pure Ag catalyst dripped on a glassy carbon electrode as a working electrode, a platinum wire electrode as a counter electrode and a mercury/mercury oxide electrode as a reference electrode. The catalysts were tested for cyclic voltammograms in a 1M KOH solution deoxygenated with nitrogen. The catalysts were tested for cyclic voltammograms in a 1M KOH +1M KCOOH solution deoxygenated with nitrogen. The potential window is-0.9-0.2V, and the scanning speed is 50 mV/s.
Example 6
This example is Ag50Pd50The prepared catalyst can effectively catalyze the oxidation of formate, and the peak current provided at 0.74V is 20.8mA/cm2. The preparation process of this example is as follows:
(1) 0.0348g of Apzc was weighed into 6.9mL of distilled water and stirred magnetically until dissolved sufficiently. Then 1mL of H was added to the stirred Apzc solution2PdCl4(20mmol/L) and 1mL AgNO3(20mmol/L), and stirred magnetically at room temperature for 5 min. Wherein the concentration of Apzc is 25mmol/L, H2PdCl4Has a concentration of 2mmol/L, AgNO3The concentration of (2) was 2 mmol/L.
(2) And (2) quickly injecting 1mL of ascorbic acid solution (0.1mol/L) into the precursor solution obtained in the step (1), and stirring and reacting for 1h at room temperature. Then, 0.1mL of hydrazine hydrate (80 wt%) was added, and the reaction was continued with stirring for 30 min.
(3) Centrifuging at 8000r/min, washing with distilled water and anhydrous ethanol for 3 times, and drying in a freeze drier for 12 hr to obtain flower-shaped AgPd alloy catalyst. In the catalyst H2PdCl4With AgNO3The ratio of the amount of the substance is 1:1 and is marked as Ag50Pd50。
(4) Study on electrocatalysis of formate oxidation reaction
By dropping Ag on glassy carbon electrode50Pd50The alloy catalyst is used as a working electrode, the platinum wire electrode is used as a counter electrode, and the mercury/mercury oxide electrode is used as a reference electrode, so that a three-electrode electrochemical test system is constructed. The catalysts were tested for cyclic voltammograms in a 1M KOH solution deoxygenated with nitrogen. The catalysts were tested for cyclic voltammograms in a 1M KOH +1M KCOOH solution deoxygenated with nitrogen. The potential window is-0.9-0.2V, and the scanning speed is 50 mV/s.
Example 7
This example is Ag50Pd50The prepared catalyst can effectively catalyze the oxidation of formate, and the peak current density provided at 0.75V is 25.2mA/cm2. The preparation process of this example is as follows:
(1) 0.0348g of Apzc was weighed into 6.9mL of distilled water and stirred magnetically until dissolved sufficiently. Then, 1mL of Pd (NO) was added to each of the stirred Apzc solutions3)2(20mmol/L) and 1mL AgNO3(20mmol/L), and stirred magnetically at room temperature for 5 min. Wherein the concentration of Apzc is 25mmol/L, Pd (NO)3)2Has a concentration of 2mmol/L, AgNO3The concentration of (2) was 2 mmol/L.
(2) And (2) quickly injecting 1mL of ascorbic acid solution (0.1mol/L) into the precursor solution obtained in the step (1), and stirring and reacting for 1h at room temperature. Then, 0.1mL of hydrazine hydrate (80 wt%) was added, and the reaction was continued with stirring for 30 min.
(3) And (3) performing centrifugal separation at 8000r/min, washing with distilled water and absolute ethyl alcohol for 3 times respectively, and finally drying the washed product in a freeze dryer for 12 hours to obtain the AgPd nano alloy catalyst. Pd (NO) in the catalyst3)2With AgNO3The ratio of the amount of the substance is 1:1 and is marked as Ag50Pd50。
(4) Study on electrocatalysis of formate oxidation reaction
By dropping Ag on glassy carbon electrode50Pd50The nano alloy catalyst is used as a working electrode, the platinum wire electrode is used as a counter electrode, and the mercury/mercury oxide electrode is used as a reference electrode, so that a three-electrode electrochemical test system is constructed. The catalysts were tested for cyclic voltammograms in a 1M KOH solution deoxygenated with nitrogen. The catalysts were tested for cyclic voltammograms in a 1M KOH +1M KCOOH solution deoxygenated with nitrogen. The potential window is-0.9-0.2V, and the scanning speed is 50 mV/s.
Claims (4)
1. A preparation method of flower-shaped AgPd nano alloy for formate oxidation reaction electrocatalysis and surface plasma catalysis is characterized in that: the flower-shaped AgPd nano alloy comprises the following components in atomic percentage: 25-75% of silver and 25-75% of palladium; the average particle size is 320 nm;
the preparation method comprises the following specific steps:
step 1: adding 3-aminopyrazine-2-carboxylic acid (Apzc) into distilled water, and magnetically stirring until the solution is fully dissolved; palladium salt and silver nitrate (AgNO) are then added to the stirred Apzc solution3) Magnetically stirring at room temperature for 5 min;
in the solution: the concentration of Apzc is 10-60 mmol/L, and the palladium salt and AgNO are34mmol/L, palladium salt: AgNO3The amount ratio of the substances (A) to (B) is 1: 0-3;
step 2: then adding 1mL of ascorbic acid solution, and stirring and reacting for 0.5-2 h at room temperature; then adding 0.1mL of hydrazine hydrate solution, and continuously stirring for reaction for 10-50 min;
the concentration of the ascorbic acid solution is 0.1 mol/L;
the mass fraction of hydrazine hydrate in the hydrazine hydrate solution is 80 percent;
and step 3: centrifuging at 6000-10000 r/min, washing with distilled water and absolute ethyl alcohol for 3 times respectively, and finally drying the washed product in a freeze dryer for 8-20 h to obtain the flower-shaped AgPd nano alloyGold; the electrochemical specific surface area of the flower-shaped AgPd nano alloy is 3.79-10.37 m2/g。
2. The method for preparing flower-like AgPd nano-alloy for formate oxidation reaction electrocatalysis and surface plasma catalysis according to claim 1, characterized in that: the palladium salt is sodium tetrachloropalladate Na2PdCl4Chloropalladate H2PdCl4Or palladium nitrate Pd (NO3)2。
3. The method for preparing the flower-like AgPd nano-alloy for formate oxidation reaction electrocatalysis and surface plasma catalysis according to claim 2, characterized in that: the palladium chloride acid is PdCl2Ultrasonic dissolving in HCl solution to obtain H2PdCl4。
4. The method for preparing flower-like AgPd nano-alloy for formate oxidation reaction electrocatalysis and surface plasma catalysis according to claim 3, characterized in that: the concentration of the HCl solution is 0.1 mol/L.
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