CN107175105B - Preparation method of graphene-supported palladium-iridium nanoparticle catalyst and its electrocatalytic application for formic acid oxidation - Google Patents
Preparation method of graphene-supported palladium-iridium nanoparticle catalyst and its electrocatalytic application for formic acid oxidation Download PDFInfo
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- CN107175105B CN107175105B CN201710353337.4A CN201710353337A CN107175105B CN 107175105 B CN107175105 B CN 107175105B CN 201710353337 A CN201710353337 A CN 201710353337A CN 107175105 B CN107175105 B CN 107175105B
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 74
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 59
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 230000003647 oxidation Effects 0.000 title claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 211
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 88
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 79
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 55
- 239000000243 solution Substances 0.000 claims abstract description 28
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- 239000011734 sodium Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910000575 Ir alloy Inorganic materials 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 239000000956 alloy Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 5
- 238000009210 therapy by ultrasound Methods 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 8
- 238000002484 cyclic voltammetry Methods 0.000 description 8
- 239000000446 fuel Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- 231100000086 high toxicity Toxicity 0.000 description 3
- 238000007171 acid catalysis Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- MOGGVIXWTIOANP-UHFFFAOYSA-N [O].OC=O Chemical compound [O].OC=O MOGGVIXWTIOANP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010351 charge transfer process Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- -1 iridium metals Chemical class 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
-
- 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
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- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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Abstract
本发明属于负载型催化剂制备技术领域，具体涉及一种石墨烯负载钯铱纳米颗粒催化剂制备方法及其甲酸氧化电催化应用。所述方法包括以下步骤：1)将石墨烯添加到甲酸溶液中超声混合均匀；2)氯铱酸和氯钯酸钠配制的混合溶液超声条件下分散均匀；3)将步骤2)所得混合溶液加热；4)将步骤3)所得混合溶液快速注入到步骤1)石墨烯和甲酸的混合溶液中，在密封条件下进行超声处理；5)所得产物经清洗后干燥，即可。所述催化剂具有很高的电化学活性比表面积和甲酸氧化催化活性，并且该方法不涉及高毒性材料的使用，操作简便，重复性高，适合大规模生产。
The invention belongs to the technical field of the preparation of supported catalysts, and in particular relates to a preparation method of a graphene-supported palladium iridium nanoparticle catalyst and its formic acid oxidation electrocatalysis application. The method comprises the following steps: 1) adding graphene to the formic acid solution and mixing uniformly by ultrasonic; 2) dispersing the mixed solution prepared by chloroiridic acid and sodium chloropalladate uniformly under ultrasonic conditions; 3) mixing the obtained mixed solution in step 2). Heating; 4) Quickly inject the mixed solution obtained in step 3) into the mixed solution of graphene and formic acid in step 1), and perform ultrasonic treatment under sealing conditions; 5) The obtained product is washed and dried. The catalyst has high electrochemical activity specific surface area and formic acid oxidation catalytic activity, and the method does not involve the use of highly toxic materials, has simple operation, high repeatability, and is suitable for large-scale production.
Description
Technical field
The invention belongs to loaded catalyst preparation technical fields, and in particular to a kind of graphene-supported palladium iridium nano particle
Method for preparing catalyst and its Oxidation of Formic Acid electro-catalysis application.
Background technique
It is high, environmental-friendly by the direct methanoic acid fuel cell energy conversion efficiency of fuel of liquid formic acid, as automobile
Power and portable power etc. show huge application potential.Oxidation of Formic Acid is must as direct methanoic acid fuel cell
Indispensable anode-catalyzed reaction.For at present, common palladium/carbon catalyst is not excellent enough to Oxidation of Formic Acid catalytic activity
It is difficult to meet the needs of Current commercial.For the commercialization process for accelerating direct methanoic acid fuel cell, research and preparation high-performance
Oxidation of Formic Acid catalyst is particularly important.It is compared with palladium, iridium metals price is relatively cheap, and iridium is to the chemical stability of acid
High is also most corrosion resistant metal.Suitable iridium is added into palladium not only can change the original electronic structure of palladium and surface knot
Structure reduces while reducing Oxidation of Formic Acid reaction activity to the absorption of species is poisoned, to show higher catalytic
Energy.
Catalysis reaction is related to catalyst granules surface and interface charge transfer process.The nano particle of small particle clean surface is not only
Specific surface area and utilization rate with superelevation, while effective progress that more active sites promote catalysis reaction can be shown
With the raising of kinetics of electrode process.The preparation of the uniform palladium iridium alloy particle of current small particle generally requires living by means of surface
Property agent (such as polyvinylpyrrolidone, cetyl trimethylammonium bromide) and highly toxic reducing agent (such as sodium borohydride,
Oleyl amine, hydrazine hydrate) etc..Since the metal nanoparticle surface that surfactant is easy to be coated on preparation is difficult to clean off, to cover
Cover active site causes catalytic performance to be unable to give full play；And the use of high toxicity reducing agent, it be easy to cause environmental pollution
And there are security risks.In addition, graphene has the specific surface area of excellent conduction and mechanical performance and superelevation, to help
In the effective progress for reducing charge transfer resistance and mass transport process, obtained in terms of as fuel-cell catalyst carrier wide
General application.
Therefore, studying a kind of green method easy to operate, being suitble to large-scale production, carrier surface is clean on the surface of graphene
Only, extra small and evenly dispersed palladium iridium nano particle is as Oxidation of Formic Acid catalyst, for accelerating the quotient of direct methanoic acid fuel cell
Industryization development is of great significance.
Summary of the invention
In consideration of it, the purpose of the present invention is to provide ultrasonic assistance method, to prepare graphene-supported clean surface extra small and uniform
Disperse the method for palladium iridium nanoparticle catalyst, the catalyst of preparation has very high electrochemically active specific surface area and formic acid oxygen
Change catalytic activity, and this method is not related to the use of high toxicity material, easy to operate, repeatability is high, is suitble to large-scale production.
The technical solution adopted by the invention is as follows:
A kind of preparation method of graphene-supported palladium iridium nanoparticle catalyst, comprising the following steps:
1) that graphene is added to ultrasonic mixing in formic acid solution is uniform；
2) it is uniformly dispersed under the mixed solution ultrasound condition that chloro-iridic acid and chlorine palladium acid sodium are prepared；
3) mixed solution obtained by step 2) is heated；
4) mixed solution obtained by step 3) is rapidly injected in the mixed solution of step 1) graphene and formic acid, is being sealed
Under the conditions of be ultrasonically treated；
5) the once purged drying of products therefrom.
In the step 1), concentration of the graphene in formic acid solution is 1~5mg/mL, and ultrasound is carried out at 75-95 DEG C
Processing.
In the step 2), the molar ratio of palladium and iridium is 1:1~4:1.
In the step 2), ultrasonic time is 0.5h~5h, and power is 100~600W.
In the step 3), solution is heated to 60 DEG C~95 DEG C.
In the step 4), the mass ratio of palladium iridium alloy and graphene is 1:5~1:1.
It in the step 4), is ultrasonically treated under 60 DEG C~95 DEG C air-proof conditions, ultrasonic time is 2h~10h, function
Rate is 100~600W.
In the step 5), drying temperature is 40 DEG C~100 DEG C, and the time is 10~20h.
The graphene-supported palladium iridium nanoparticle catalyst that the method is prepared.
Application of the graphene-supported palladium iridium nanoparticle catalyst in Oxidation of Formic Acid electrocatalytic reaction.
Palladium iridium/graphene prepared by the present invention has bigger electro-chemical activity ratio compared with being commercialized palladium/carbon catalyst
Surface area and higher Oxidation of Formic Acid catalytic activity, alternative commercialization palladium/carbon catalyst are applied to direct methanoic acid fuel cell
And other energy conversion fields, have higher practical value；And the method for the present invention is not related to the use of high toxicity material,
Easy to operate, repeatability is high, can expand and prepare other nano particles and have broad field of application and prospect.
Detailed description of the invention
In order to keep the purpose of the present invention, technical scheme and beneficial effects clearer, the present invention provides following attached drawing and carries out
Illustrate:
Fig. 1 is palladium iridium/graphen catalyst transmission electron microscope picture prepared by embodiment 1；
Fig. 2 is palladium iridium/graphen catalyst prepared by embodiment 1 and commercialization palladium/carbon catalyst in 0.5M H2SO4Solution
In cyclic voltammetry curve compare figure；
Fig. 3 is palladium iridium/graphen catalyst prepared by embodiment 1 and commercialization palladium/carbon catalyst in 0.5M H2SO4+
Catalytic activity in 0.5M HCOOH solution compares figure；
Fig. 4 is palladium iridium/graphen catalyst transmission electron microscope picture prepared by embodiment 2；
Fig. 5 is palladium iridium/graphen catalyst prepared by embodiment 2 and commercialization palladium/carbon catalyst in 0.5M H2SO4Solution
In cyclic voltammetry curve compare figure；
Fig. 6 is palladium iridium/graphen catalyst prepared by embodiment 2 and commercialization palladium/carbon catalyst in 0.5M H2SO4+
Catalytic activity in 0.5M HCOOH solution compares figure；
Fig. 7 is palladium iridium/- 1 catalyst of graphene transmission electron microscope picture prepared by embodiment 3；
Fig. 8 is palladium iridium/- 1 catalyst of graphene prepared by embodiment 3 and commercialization palladium/carbon catalyst in 0.5M H2SO4It is molten
Cyclic voltammetry curve in liquid compares figure；
Fig. 9 is palladium iridium/- 1 catalyst of graphene prepared by embodiment 3 and commercialization palladium/carbon catalyst in 0.5M H2SO4+
Catalytic activity in 0.5M HCOOH solution compares figure；
Figure 10 is palladium iridium/- 2 catalyst of graphene transmission electron microscope picture prepared by embodiment 4；
Figure 11 is palladium iridium/- 2 catalyst of graphene prepared by embodiment 4 and commercialization palladium/carbon catalyst in 0.5M H2SO4
Cyclic voltammetry curve in solution compares figure；
Figure 12 is palladium iridium/- 2 catalyst of graphene prepared by embodiment 4 and commercialization palladium/carbon catalyst in 0.5M H2SO4+
Catalytic activity in 0.5M HCOOH solution compares figure.
Specific embodiment
Below in conjunction with attached drawing, a preferred embodiment of the present invention will be described in detail.
Embodiment 1
The palladium iridium of the present embodiment/graphene high-performance Oxidation of Formic Acid catalyst preparation method, comprising the following steps:
1) 15mg graphene is added in 8mL formic acid solution at 90 DEG C to ultrasonic mixing is uniform, ultrasonic power 300W.
2) 0.286mL chloro-iridic acid (7mgmL-1 Ir) and 0.221mL chlorine palladium acid sodium (20mgmL-1 Pd) prepare mixing it is molten
Liquid ultrasound 1h, ultrasonic power 300W.
3) solution of the step 2) ultrasonic mixing after uniform is heated to 90 DEG C.
4) step 3) mixed solution is rapidly injected in the mixed solution of step 1) graphene and formic acid, is sealed at 90 DEG C
Under the conditions of carry out ultrasonic treatment 5h, ultrasonic power 300W.
5) 60 DEG C of dry 10h after the product cleaning that reaction obtains, as palladium iridium/graphene high-performance Oxidation of Formic Acid catalysis
Agent.
Fig. 1 is palladium iridium/graphen catalyst transmission electron microscope picture prepared by embodiment 1；Can clearly it find out from figure
Extra small palladium iridium alloy even particulate dispersion on the surface of graphene on, average grain diameter is in 3.4 rans.
Fig. 2 is palladium iridium/graphen catalyst prepared by embodiment 1 and commercialization palladium/carbon catalyst in 0.5M H2SO4Solution
In cyclic voltammetry curve compare figure；It was found that comparing (26.6m with commercialization palladium/carbon catalyst2g-1), palladium prepared by embodiment 1
Iridium/graphen catalyst shows higher electrochemically active specific surface area (76.3m2g-1), illustrate palladium prepared by embodiment 1
Iridium/graphen catalyst has more active sites.
Fig. 3 is palladium iridium/graphen catalyst prepared by embodiment 1 and commercialization palladium/carbon catalyst in 0.5M H2SO4+
Current density in 0.5M HCOOH solution compares figure；It was found that comparing (286.1mA mg with commercialization palladium/carbon catalyst-1 metal), palladium iridium/graphen catalyst prepared by embodiment 1 shows higher peak current density (576.4mA mg-1 metal),
Simultaneously in the case where just inswept journey is with uniform current density in have more negative electrode potential, illustrate embodiment 1 prepare palladium iridium/graphene
Catalyst has higher Oxidation of Formic Acid catalytic activity.
Above-mentioned experimental data shows that palladium iridium/graphen catalyst prepared by embodiment 1 has more Oxidation of Formic Acid activity
Specific surface area and higher catalytic activity, so that alternative commercialization palladium/carbon catalyst is applied to direct methanoic acid fuel cell
And other energy conversion fields.
Embodiment 2
The palladium iridium of the present embodiment/graphene high-performance Oxidation of Formic Acid catalyst preparation method, comprising the following steps:
1) 15mg graphene is added in 5mL formic acid solution at 80 DEG C to ultrasonic mixing is uniform, ultrasonic power 300W.
2) 0.286mL chloro-iridic acid (7mgmL-1 Ir) and 0.221mL chlorine palladium acid sodium (20mgmL-1 Pd) prepare mixing it is molten
Liquid ultrasound 2h, ultrasonic power 500W.
3) solution of the step 2) ultrasonic mixing after uniform is heated to 80 DEG C.
4) step 3) mixed solution is rapidly injected in the mixed solution of step 1) graphene and formic acid, is sealed at 80 DEG C
Under the conditions of carry out ultrasonic treatment 8h, ultrasonic power 500W.
5) 80 DEG C of dry 16h after the product cleaning that reaction obtains, as palladium iridium/graphene high-performance Oxidation of Formic Acid catalysis
Agent.
Fig. 4 is palladium iridium/graphen catalyst transmission electron microscope picture prepared by embodiment 2；Can clearly it find out from figure
Extra small palladium iridium alloy even particulate dispersion on the surface of graphene on, average grain diameter is in 3.6 rans.
Fig. 5 is palladium iridium/graphen catalyst prepared by embodiment 2 and commercialization palladium/carbon catalyst in 0.5M H2SO4Solution
In cyclic voltammetry curve compare figure；It was found that comparing (26.6m with commercialization palladium/carbon catalyst2g-1), palladium prepared by embodiment 2
Iridium/graphen catalyst shows higher electrochemically active specific surface area (74.6m2g-1), illustrate palladium prepared by embodiment 2
Iridium/graphen catalyst has more active sites.
Fig. 6 is palladium iridium/graphen catalyst prepared by embodiment 2 and commercialization palladium/carbon catalyst in 0.5M H2SO4+
Current density in 0.5M HCOOH solution compares figure；It was found that comparing (286.1mA mg with commercialization palladium/carbon catalyst-1 metal), palladium iridium/graphen catalyst prepared by embodiment 2 shows higher peak current density (509.9mA mg-1 metal),
Simultaneously in the case where just inswept journey is with uniform current density in have more negative electrode potential, illustrate embodiment 2 prepare palladium iridium/graphene
Catalyst has higher Oxidation of Formic Acid catalytic activity.
Above-mentioned experimental data shows that palladium iridium/graphen catalyst prepared by embodiment 2 has more Oxidation of Formic Acid activity
Specific surface area and higher catalytic activity, so that alternative commercialization palladium/carbon catalyst is applied to direct methanoic acid fuel cell
And other energy conversion fields.
Embodiment 3
The palladium iridium of the present embodiment/graphene Oxidation of Formic Acid catalyst preparation method, comprising the following steps:
1) 15mg graphene is added in 8mL sodium borohydride aqueous solution (2mg/mL) at 90 DEG C to ultrasonic mixing is uniform,
Ultrasonic power is 300W.
2) 0.286mL chloro-iridic acid (7mgmL-1 Ir) and 0.221mL chlorine palladium acid sodium (20mgmL-1 Pd) prepare mixing it is molten
Liquid ultrasound 1h, ultrasonic power 300W.
3) solution of the step 2) ultrasonic mixing after uniform is heated to 90 DEG C.
4) step 3) mixed solution is rapidly injected in the mixed solution of step 1) graphene and sodium borohydride, at 90 DEG C
Ultrasonic treatment 5h, ultrasonic power 300W are carried out under air-proof condition.
5) 60 DEG C of dry 10h, as -1 Oxidation of Formic Acid catalyst of palladium iridium/graphene after the product cleaning that reaction obtains.
Fig. 7 is palladium iridium/- 1 catalyst of graphene transmission electron microscope picture prepared by embodiment 3；It can be clearly from figure
Out in the dispersion on the surface of graphene of palladium iridium alloy particle, but its particle size span is big, inhomogenous.
Fig. 8 is palladium iridium/- 1 catalyst of graphene prepared by embodiment 3 and commercialization palladium/carbon catalyst in 0.5M H2SO4It is molten
Cyclic voltammetry curve in liquid compares figure；It was found that comparing (26.6m with commercialization palladium/carbon catalyst2g-1), prepared by embodiment 3
- 1 catalyst of palladium/graphene shows higher electrochemically active specific surface area (49.6m2g-1), illustrate palladium prepared by embodiment 3
- 1 catalyst of iridium/graphene has more active site.
Fig. 9 is palladium iridium/- 1 catalyst of graphene prepared by embodiment 3 and commercialization palladium/carbon catalyst in 0.5M H2SO4+
Current density in 0.5M HCOOH solution compares figure；It was found that comparing (286.1mA mg with commercialization palladium/carbon catalyst-1 metal), palladium iridium/graphen catalyst prepared by embodiment 3 shows higher peak current density (374.2mA mg-1 metal),
Simultaneously in the case where just inswept journey is with uniform current density in there is relatively negative electrode potential, illustrate palladium iridium/graphene prepared by embodiment 3
Catalyst has certain Oxidation of Formic Acid catalytic activity.
Above-mentioned experimental data shows in embodiment 3 using palladium iridium/- 1 catalyst of graphene formic acid of sodium borohydride preparation
Oxidation activity specific surface area and catalytic activity are above commercialization palladium/carbon catalyst and are but below in embodiment 1 and embodiment 2
Palladium iridium/graphen catalyst of preparation.
Embodiment 4
The palladium iridium of the present embodiment/graphene Oxidation of Formic Acid catalyst preparation method, comprising the following steps:
1) 15mg graphene is added in 8mL formic acid solution at 90 DEG C to ultrasonic mixing is uniform, ultrasonic power 300W.
2) 0.286mL chloro-iridic acid (7mgmL-1 Ir) and 0.221mL chlorine palladium acid sodium (20mgmL-1 Pd) prepare mixing it is molten
Liquid ultrasound 1h, ultrasonic power 300W.
3) solution of the step 2) ultrasonic mixing after uniform is heated to 90 DEG C.
4) step 3) mixed solution is rapidly injected in the mixed solution of step 1) graphene and formic acid, is sealed at 90 DEG C
Under the conditions of be stirred 5h.
5) 60 DEG C of dry 10h, as -2 Oxidation of Formic Acid catalyst of palladium iridium/graphene after the product cleaning that reaction obtains.
Figure 10 is palladium iridium/- 2 catalyst of graphene transmission electron microscope picture prepared by embodiment 4；It can be clearly from figure
Out in the dispersion on the surface of graphene of palladium iridium alloy particle, but its particle size span is big, inhomogenous.
Figure 11 is palladium iridium/- 2 catalyst of graphene prepared by embodiment 4 and commercialization palladium/carbon catalyst in 0.5M H2SO4
Cyclic voltammetry curve in solution compares figure；It was found that comparing (26.6m with commercialization palladium/carbon catalyst2g-1), it is prepared by embodiment 4
- 1 catalyst of palladium/graphene show higher electrochemically active specific surface area (46.3m2g-1), illustrate prepared by embodiment 4
Palladium iridium/- 2 catalyst of graphene has more active site.
Figure 12 is palladium iridium/- 2 catalyst of graphene prepared by embodiment 4 and commercialization palladium/carbon catalyst in 0.5M H2SO4+
Current density in 0.5M HCOOH solution compares figure；It was found that comparing (286.1mA mg with commercialization palladium/carbon catalyst-1 metal), palladium iridium/- 2 catalyst of graphene prepared by embodiment 4 shows higher peak current density (350.2mA mg-1 metal), while in the case where just inswept journey is with uniform current density in there is relatively negative electrode potential, illustrate palladium prepared by embodiment 4
- 2 alkene catalyst of iridium/graphite has certain Oxidation of Formic Acid catalytic activity.
Above-mentioned experimental data shows to urge in step 4) without palladium iridium/graphene -2 prepared by the embodiment of ultrasonic treatment 4
The Oxidation of Formic Acid specific surface area active of agent and catalytic activity are above commercialization palladium/carbon catalyst and are but below embodiment 1
With the palladium iridium/graphen catalyst prepared in embodiment 2.
Finally, it is stated that preferred embodiment above is only used to illustrate the technical scheme of the present invention and not to limit it, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (6)
1. a kind of preparation method of graphene-supported palladium iridium nanoparticle catalyst, it is characterised in that: the following steps are included:
1) graphene is added to ultrasonic mixing in formic acid solution is uniform, concentration of the graphene in formic acid solution is 1~5mg/
ML is ultrasonically treated at 75-95 DEG C；
2) it is uniformly dispersed under the mixed solution ultrasound condition that chloro-iridic acid and chlorine palladium acid sodium are prepared, ultrasonic time is 0.5h~5h, function
Rate is 100~600W；
3) mixed solution obtained by step 2) is heated to 60 DEG C~95 DEG C；
4) mixed solution obtained by step 3) is rapidly injected in the mixed solution of step 1) graphene and formic acid, 60 DEG C~95
It is ultrasonically treated under DEG C air-proof condition, ultrasonic time is 2h~10h, and power is 100~600W, obtains graphene-supported palladium iridium
The catalyst of alloy；
5) the once purged drying of products therefrom.
2. the preparation method of graphene-supported palladium iridium nanoparticle catalyst according to claim 1, it is characterised in that: institute
It states in step 2), the molar ratio of palladium and iridium is 1:1~4:1.
3. the preparation method of graphene-supported palladium iridium nanoparticle catalyst according to claim 1, it is characterised in that: institute
It states in step 4), the mass ratio of palladium iridium alloy and graphene is 1:5~1:1.
4. the preparation method of graphene-supported palladium iridium nanoparticle catalyst according to claim 1, it is characterised in that: institute
It states in step 5), drying temperature is 40 DEG C~100 DEG C, and the time is 10~20h.
5. a kind of graphene-supported palladium iridium nano particle catalysis being prepared such as claim 1-4 any one the method
Agent.
6. a kind of graphene-supported palladium iridium nanoparticle catalyst as claimed in claim 5 is in Oxidation of Formic Acid electrocatalytic reaction
Application.
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| CN107175105B (en) * | 2017-05-18 | 2019-06-21 | 青岛大学 | Preparation method of graphene-supported palladium-iridium nanoparticle catalyst and its electrocatalytic application for formic acid oxidation |
| CN108346808B (en) * | 2018-03-09 | 2020-07-17 | 青岛大学 | A kind of palladium tin nano chain network catalyst and its preparation method and application |
| CN109037705B (en) * | 2018-08-01 | 2021-05-04 | 青岛大学 | Preparation method of graphene-loaded ultra-small palladium-copper nano-grade high-performance formic acid catalytic oxidant, product and application thereof |
| CN109301268B (en) * | 2018-09-29 | 2021-09-07 | 信阳师范学院 | Li-CO2 battery cathode catalyst material and preparation method thereof, battery cathode material and battery |
| CN110560124A (en) * | 2019-09-05 | 2019-12-13 | 吉林大学 | Efficient nano catalyst for hydrogen production by formic acid hydrolysis and preparation method thereof |
| CN111790449A (en) * | 2020-07-30 | 2020-10-20 | 泉州师范学院 | A kind of iridium nanoparticle catalyst and preparation method thereof and application in catalytic reduction of nitro compound into amino compound |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4490482A (en) * | 1983-03-02 | 1984-12-25 | Her Majesty The Queen In Right Of Canada | Method for producing a catalyst for oxidizing carbon monoxide |
| CN1721062A (en) * | 2005-05-25 | 2006-01-18 | 南京师范大学 | Complex reduction preparation method of highly alloyed platinum-based composite metal nanocatalyst |
| CN1921197A (en) * | 2006-08-23 | 2007-02-28 | 南京师范大学 | Ultra-fine, highly dispersed Pd/C catalyst for direct aminic acid fuel battery and method for making same |
| CN102064311A (en) * | 2010-12-08 | 2011-05-18 | 清华大学 | Preparation method of carbon nanometer tube metal particle composite |
| CN103111292A (en) * | 2013-01-22 | 2013-05-22 | 北京格林凯默科技有限公司 | Simple preparation method of palladium-based catalyst and palladium-based catalyst prepared by using same |
| CN103157519A (en) * | 2011-12-19 | 2013-06-19 | 中国科学院大连化学物理研究所 | Preparing method for supported core-shell-structure catalyst for low-temperature fuel cell |
| CN107175105A (en) * | 2017-05-18 | 2017-09-19 | 青岛大学 | Graphene-supported palladium iridium nanoparticle catalyst preparation method and its Oxidation of Formic Acid electro-catalysis application |
-
2017
- 2017-05-18 CN CN201710353337.4A patent/CN107175105B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4490482A (en) * | 1983-03-02 | 1984-12-25 | Her Majesty The Queen In Right Of Canada | Method for producing a catalyst for oxidizing carbon monoxide |
| CN1721062A (en) * | 2005-05-25 | 2006-01-18 | 南京师范大学 | Complex reduction preparation method of highly alloyed platinum-based composite metal nanocatalyst |
| CN1921197A (en) * | 2006-08-23 | 2007-02-28 | 南京师范大学 | Ultra-fine, highly dispersed Pd/C catalyst for direct aminic acid fuel battery and method for making same |
| CN102064311A (en) * | 2010-12-08 | 2011-05-18 | 清华大学 | Preparation method of carbon nanometer tube metal particle composite |
| CN103157519A (en) * | 2011-12-19 | 2013-06-19 | 中国科学院大连化学物理研究所 | Preparing method for supported core-shell-structure catalyst for low-temperature fuel cell |
| CN103111292A (en) * | 2013-01-22 | 2013-05-22 | 北京格林凯默科技有限公司 | Simple preparation method of palladium-based catalyst and palladium-based catalyst prepared by using same |
| CN107175105A (en) * | 2017-05-18 | 2017-09-19 | 青岛大学 | Graphene-supported palladium iridium nanoparticle catalyst preparation method and its Oxidation of Formic Acid electro-catalysis application |
Non-Patent Citations (2)
| Title |
|---|
| "Facile preparation of PdIr alloy nano-electrocatalysts supported on carbon nanotubes, and their enhanced performance in the electro-oxidation of formic acid";Yanfei Hao等;《international journal of hydrogen energy》;20151217;第41卷;3015-3022 * |
| "One-pot wet-chemical synthesis of PtPd@Pt nanocrystals supported on reduced graphene oxide with highly electrocatalytic performance for ethylene glycol oxidation";Lei Liu等;《Electrochimica Acta》;20151202;第187卷;576–583 * |
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