CN107175105A - Graphene-supported palladium iridium nanoparticle catalyst preparation method and its Oxidation of Formic Acid electro-catalysis application - Google Patents
Graphene-supported palladium iridium nanoparticle catalyst preparation method and its Oxidation of Formic Acid electro-catalysis application Download PDFInfo
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- CN107175105A CN107175105A CN201710353337.4A CN201710353337A CN107175105A CN 107175105 A CN107175105 A CN 107175105A CN 201710353337 A CN201710353337 A CN 201710353337A CN 107175105 A CN107175105 A CN 107175105A
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- formic acid
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 213
- 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 103
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 89
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 77
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 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 22
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 21
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 50
- 239000000243 solution Substances 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 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
- 239000000460 chlorine Substances 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 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
- 238000002604 ultrasonography Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910000575 Ir alloy Inorganic materials 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 231100000086 high toxicity Toxicity 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 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
- 150000007513 acids Chemical class 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- 238000007171 acid catalysis Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000006185 dispersion 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
- 238000005516 engineering process Methods 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
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 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
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- 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
-
- 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
- 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
- B01J35/613—10-100 m2/g
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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
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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Abstract
The invention belongs to loaded catalyst preparing technical field, and in particular to a kind of graphene-supported palladium iridium nanoparticle catalyst preparation method and its Oxidation of Formic Acid electro-catalysis application.It the described method comprises the following steps：1) that graphene is added into ultrasonic mixing in formic acid solution is uniform；2) it is uniformly dispersed under the mixed solution ultrasound condition that chloro-iridic acid and the sour sodium of chlorine palladium are prepared；3) by step 2) gained mixed solution heating；4) by step 3) gained mixed solution is rapidly injected step 1) in the mixed solution of graphene and formic acid, carried out under air-proof condition ultrasonically treated；5) the once purged drying of products therefrom, you can.The catalyst is with very high electrochemically active specific surface area and Oxidation of Formic Acid catalytic activity, and this method is not related to the use of high toxicity material, easy to operate, and repeatability is high, is adapted to large-scale production.
Description
Technical field
The invention belongs to loaded catalyst preparing technical field, 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 technology
Direct methanoic acid fuel cell energy conversion efficiency by fuel of liquid formic acid is high, environment-friendly, is being used as automobile
Huge application potential is shown in terms of power and compact power.Oxidation of Formic Acid is must as direct methanoic acid fuel cell
Indispensable anode-catalyzed reaction.For at present, its conventional palladium/carbon catalyst is not excellent enough to Oxidation of Formic Acid catalytic activity
It is difficult to the need for meeting Current commercial.To accelerate the commercialization process of direct methanoic acid fuel cell, research and preparation high-performance
Oxidation of Formic Acid catalyst is particularly important.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.Appropriate iridium is added into palladium can not only change the original electronic structure of palladium and surface knot
Structure, reduction is to poisoning the absorption of species while Oxidation of Formic Acid reaction activity is reduced, so as to show higher catalytic
Energy.
Catalytic 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 avtive spots promote catalytic 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 to be lived 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..Because the metal nanoparticle surface that surfactant is easily coated on preparation is difficult to clean off, so as to cover
Cover avtive spot causes catalytic performance not give full play to；And the use of high toxicity reducing agent, easily cause environmental pollution
And there is potential safety hazard.In addition, graphene has excellent conduction and mechanical performance and the specific surface area of superelevation, so as to help
In effective progress of reduction charge transfer resistance and mass transport process, obtain wide in terms of as fuel-cell catalyst carrier
General application.
Therefore, a kind of green method easy to operate, being adapted to large-scale production is studied clean in graphenic surface carrier surface
Only, extra small and dispersed palladium iridium nano particle is as Oxidation of Formic Acid catalyst, the business for accelerating direct methanoic acid fuel cell
Industryization development is significant.
The content of the invention
In consideration of it, it is extra small and uniform to prepare graphene-supported clean surface it is an object of the invention to provide ultrasonic assistance method
The method of scattered 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, and easy to operate, repeatability is high, is adapted to large-scale production.
The technical solution adopted by the present invention is as follows：
A kind of preparation method of graphene-supported palladium iridium nanoparticle catalyst, comprises the following steps：
1) that graphene is added into ultrasonic mixing in formic acid solution is uniform；
2) it is uniformly dispersed under the mixed solution ultrasound condition that chloro-iridic acid and the sour sodium of chlorine palladium are prepared；
3) by step 2) gained mixed solution heating；
4) by step 3) gained mixed solution is rapidly injected step 1) in the mixed solution of graphene and formic acid, in sealing
Under the conditions of carry out it is ultrasonically treated；
5) the once purged drying of products therefrom, you can.
The step 1) in, concentration of the graphene in formic acid solution is 1~5mg/mL, ultrasonic in being carried out at 75-95 DEG C
Processing.
The step 2) in, the mol ratio of palladium and iridium is 1:1~4:1.
The step 2) in, ultrasonic time is 0.5h~5h, and power is 100~600W.
The step 3) in, solution is heated to 60 DEG C~95 DEG C.
The step 4) in, the mass ratio of palladium iridium alloy and graphene is 1:5~1:1.
The step 4) in, carried out under 60 DEG C~95 DEG C air-proof conditions it is ultrasonically treated, ultrasonic time be 2h~10h, work(
Rate is 100~600W.
The step 5) in, drying temperature is 40 DEG C~100 DEG C, and the time is 10~20h.
The graphene-supported palladium iridium nanoparticle catalyst that methods described is prepared.
Application of the described graphene-supported palladium iridium nanoparticle catalyst in Oxidation of Formic Acid electrocatalytic reaction.
Palladium iridium/graphene prepared by the present invention is compared with being commercialized palladium/carbon catalyst, with bigger electro-chemical activity ratio
The Oxidation of Formic Acid catalytic activity of surface area and Geng Gao, alternative commercialization palladium/carbon catalyst is applied to direct methanoic acid fuel cell
And other energy conversion fields, possess higher practical value；And the inventive method is not related to the use of high toxicity material,
Easy to operate, repeatability is high, can expand and prepare other nano particles and with broad field of application and prospect.
Brief description of the drawings
In order that the purpose of the present invention, technical scheme and beneficial effect are clearer, the present invention provides drawings described below and carried out
Explanation：
Fig. 1 is the transmission electron microscope picture of palladium iridium/graphen catalyst 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 the transmission electron microscope picture of palladium iridium/graphen catalyst 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 the transmission electron microscope picture of palladium iridium/catalyst of graphene -1 prepared by embodiment 3；
Fig. 8 is palladium iridium/catalyst of graphene -1 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/catalyst of graphene -1 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 the transmission electron microscope picture of palladium iridium/catalyst of graphene -2 prepared by embodiment 4；
Figure 11 is palladium iridium/catalyst of graphene -2 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/catalyst of graphene -2 prepared by embodiment 4 and commercialization palladium/carbon catalyst in 0.5M H2SO4+
Catalytic activity in 0.5M HCOOH solution compares figure.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.
Embodiment 1
The preparation method of the palladium iridium of the present embodiment/graphene high-performance Oxidation of Formic Acid catalyst, comprises the following steps：
1) 15mg graphenes are added in 8mL formic acid solutions at 90 DEG C to ultrasonic mixing is uniform, ultrasonic power is 300W.
2) 0.286mL chloro-iridic acids (7mgmL-1 Ir) and the sour sodium (20mgmL of 0.221mL chlorine palladium-1 Pd) prepare mixing it is molten
Liquid ultrasound 1h, ultrasonic power is 300W.
3) by step 2) solution after ultrasonic mixing is uniform is heated to 90 DEG C.
4) by step 3) mixed solution is rapidly injected step 1) in the mixed solution of graphene and formic acid, in 90 DEG C of sealings
Under the conditions of carry out ultrasonically treated 5h, ultrasonic power is 300W.
5) 60 DEG C of dry 10h after the product cleaning that reaction is obtained, as palladium iridium/graphene high-performance Oxidation of Formic Acid catalysis
Agent.
Fig. 1 is the transmission electron microscope picture of palladium iridium/graphen catalyst prepared by embodiment 1；Can clearly it find out from figure
Extra small palladium iridium alloy even particulate dispersion is on graphenic surface, and 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),
There is more negative electrode potential under just inswept journey is with uniform current density simultaneously, illustrate palladium iridium/graphene prepared by embodiment 1
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 preparation method of the palladium iridium of the present embodiment/graphene high-performance Oxidation of Formic Acid catalyst, comprises the following steps：
1) 15mg graphenes are added in 5mL formic acid solutions at 80 DEG C to ultrasonic mixing is uniform, ultrasonic power is 300W.
2) 0.286mL chloro-iridic acids (7mgmL-1 Ir) and the sour sodium (20mgmL of 0.221mL chlorine palladium-1 Pd) prepare mixing it is molten
Liquid ultrasound 2h, ultrasonic power is 500W.
3) by step 2) solution after ultrasonic mixing is uniform is heated to 80 DEG C.
4) by step 3) mixed solution is rapidly injected step 1) in the mixed solution of graphene and formic acid, in 80 DEG C of sealings
Under the conditions of carry out ultrasonically treated 8h, ultrasonic power is 500W.
5) 80 DEG C of dry 16h after the product cleaning that reaction is obtained, as palladium iridium/graphene high-performance Oxidation of Formic Acid catalysis
Agent.
Fig. 4 is the transmission electron microscope picture of palladium iridium/graphen catalyst prepared by embodiment 2；Can clearly it find out from figure
Extra small palladium iridium alloy even particulate dispersion is on graphenic surface, and 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),
There is more negative electrode potential under just inswept journey is with uniform current density simultaneously, illustrate palladium iridium/graphene prepared by embodiment 2
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 preparation method of the palladium iridium of the present embodiment/graphene Oxidation of Formic Acid catalyst, comprises the following steps：
1) that 15mg graphenes are added in 8mL sodium borohydride aqueous solutions (2mg/mL) at 90 DEG C into ultrasonic mixing is uniform,
Ultrasonic power is 300W.
2) 0.286mL chloro-iridic acids (7mgmL-1 Ir) and the sour sodium (20mgmL of 0.221mL chlorine palladium-1 Pd) prepare mixing it is molten
Liquid ultrasound 1h, ultrasonic power is 300W.
3) by step 2) solution after ultrasonic mixing is uniform is heated to 90 DEG C.
4) by step 3) mixed solution is rapidly injected step 1) in the mixed solution of graphene and sodium borohydride, at 90 DEG C
Ultrasonically treated 5h is carried out under air-proof condition, ultrasonic power is 300W.
5) 60 DEG C of dry 10h, as palladium iridium/Oxidation of Formic Acid catalyst of graphene -1 after the product cleaning that reaction is obtained.
Fig. 7 is the transmission electron microscope picture of palladium iridium/catalyst of graphene -1 prepared by embodiment 3；Can be clearly from figure
Go out palladium iridium alloy particle to be dispersed on graphenic surface, but its particle size span is big, heterogeneity.
Fig. 8 is palladium iridium/catalyst of graphene -1 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
The catalyst of palladium/graphene -1 shows higher electrochemically active specific surface area (49.6m2g-1), illustrate palladium prepared by embodiment 3
Iridium/catalyst of graphene -1 has more active site.
Fig. 9 is palladium iridium/catalyst of graphene -1 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),
There is relatively negative electrode potential under just inswept journey is with uniform current density simultaneously, illustrate palladium iridium/graphene prepared by embodiment 3
Catalyst has certain Oxidation of Formic Acid catalytic activity.
Above-mentioned experimental data shows, the formic acid of palladium iridium/catalyst of graphene -1 of sodium borohydride preparation is used in embodiment 3
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 preparation method of the palladium iridium of the present embodiment/graphene Oxidation of Formic Acid catalyst, comprises the following steps：
1) 15mg graphenes are added in 8mL formic acid solutions at 90 DEG C to ultrasonic mixing is uniform, ultrasonic power is 300W.
2) 0.286mL chloro-iridic acids (7mgmL-1 Ir) and the sour sodium (20mgmL of 0.221mL chlorine palladium-1 Pd) prepare mixing it is molten
Liquid ultrasound 1h, ultrasonic power is 300W.
3) by step 2) solution after ultrasonic mixing is uniform is heated to 90 DEG C.
4) by step 3) mixed solution is rapidly injected step 1) in the mixed solution of graphene and formic acid, in 90 DEG C of sealings
Under the conditions of be stirred 5h.
5) 60 DEG C of dry 10h, as palladium iridium/Oxidation of Formic Acid catalyst of graphene -2 after the product cleaning that reaction is obtained.
Figure 10 is the transmission electron microscope picture of palladium iridium/catalyst of graphene -2 prepared by embodiment 4；Can be clearly from figure
Go out palladium iridium alloy particle to be dispersed on graphenic surface, but its particle size span is big, heterogeneity.
Figure 11 is palladium iridium/catalyst of graphene -2 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
The catalyst of palladium/graphene -1 show higher electrochemically active specific surface area (46.3m2g-1), illustrate prepared by embodiment 4
Palladium iridium/catalyst of graphene -2 has more active site.
Figure 12 is palladium iridium/catalyst of graphene -2 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/catalyst of graphene -2 prepared by embodiment 4 shows higher peak current density (350.2mA mg-1 metal), while having relatively negative electrode potential under just inswept journey is with uniform current density, illustrate palladium prepared by embodiment 4
Iridium/alkene catalyst of graphite -2 has certain Oxidation of Formic Acid catalytic activity.
Above-mentioned experimental data shows, step 4) in palladium iridium/graphene -2 for being prepared without ultrasonically treated embodiment 4 urge
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 illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
Cross above preferred embodiment the present invention is described in detail, it is to be understood by those skilled in the art 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 (10)
1. a kind of preparation method of graphene-supported palladium iridium nanoparticle catalyst, it is characterised in that：Comprise the following steps：
1) that graphene is added into ultrasonic mixing in formic acid solution is uniform；
2) it is uniformly dispersed under the mixed solution ultrasound condition that chloro-iridic acid and the sour sodium of chlorine palladium are prepared；
3) by step 2) gained mixed solution heating；
4) by step 3) gained mixed solution is rapidly injected step 1) in the mixed solution of graphene and formic acid, in air-proof condition
Lower progress is ultrasonically treated；
5) the once purged drying of products therefrom, you can.
2. the preparation method of graphene-supported palladium iridium nanoparticle catalyst according to claim 1, it is characterised in that：Institute
State step 1) in, concentration of the graphene in formic acid solution is 1~5mg/mL, ultrasonically treated in being carried out at 75-95 DEG C.
3. the preparation method of graphene-supported palladium iridium nanoparticle catalyst according to claim 1, it is characterised in that：Institute
State step 2) in, the mol ratio of palladium and iridium is 1:1~4:1.
4. the preparation method of the graphene-supported palladium iridium nanoparticle catalyst according to claim 1 or 3, its feature exists
In：The step 2) in, ultrasonic time is 0.5h~5h, and power is 100~600W.
5. the preparation method of graphene-supported palladium iridium nanoparticle catalyst according to claim 1, it is characterised in that：Institute
State step 3) in, solution is heated to 60 DEG C~95 DEG C.
6. the preparation method of graphene-supported palladium iridium nanoparticle catalyst according to claim 1, it is characterised in that：Institute
State step 4) in, the mass ratio of palladium iridium alloy and graphene is 1:5~1:1.
7. the preparation method of the graphene-supported palladium iridium nanoparticle catalyst according to claim 1 or 6, its feature exists
In：The step 4) in, carried out under 60 DEG C~95 DEG C air-proof conditions ultrasonically treated, ultrasonic time is 2h~10h, and power is
100~600W.
8. the preparation method of graphene-supported palladium iridium nanoparticle catalyst according to claim 1, it is characterised in that：Institute
State step 5) in, drying temperature is 40 DEG C~100 DEG C, and the time is 10~20h.
9. a kind of graphene-supported palladium iridium nano particle catalysis prepared such as claim 1-8 any one methods describeds
Agent.
10. a kind of graphene-supported palladium iridium nanoparticle catalyst as claimed in claim 9 is in Oxidation of Formic Acid electrocatalytic reaction
In application.
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| CN111790449A (en) * | 2020-07-30 | 2020-10-20 | 泉州师范学院 | Iridium nanoparticle catalyst, preparation method thereof and application of iridium nanoparticle catalyst in catalytic reduction of nitro compound to amino compound |
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| 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 |
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