CN109621946A - Pd/C catalyst and preparation method thereof - Google Patents
Pd/C catalyst and preparation method thereof Download PDFInfo
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- CN109621946A CN109621946A CN201811550164.6A CN201811550164A CN109621946A CN 109621946 A CN109621946 A CN 109621946A CN 201811550164 A CN201811550164 A CN 201811550164A CN 109621946 A CN109621946 A CN 109621946A
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- carbon black
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000006229 carbon black Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 23
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 230000036961 partial effect Effects 0.000 claims abstract description 13
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 29
- 238000013019 agitation Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 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 description 3
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 3
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 3
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 3
- 229930003268 Vitamin C Natural products 0.000 claims description 3
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- 229910002093 potassium tetrachloropalladate(II) Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 235000019154 vitamin C Nutrition 0.000 claims description 3
- 239000011718 vitamin C Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 8
- 239000002105 nanoparticle Substances 0.000 abstract description 8
- 239000007791 liquid phase Substances 0.000 abstract description 5
- 238000009938 salting Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 229910021642 ultra pure water Inorganic materials 0.000 description 9
- 239000012498 ultrapure water Substances 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 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 5
- 206010013786 Dry skin Diseases 0.000 description 5
- 239000012901 Milli-Q water Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 235000019253 formic acid Nutrition 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 238000006619 Stille reaction Methods 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound 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
- 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
- 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
- B01J23/44—Palladium
-
- 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
-
- 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
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- 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
- B01J37/16—Reducing
-
- 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
- H01M4/925—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of Pd/C catalyst and preparation method thereof, using carbon black as carrier, Pd metal nanoparticle is dispersed on carbon black the Pd/C catalyst；The mass percentage content of Pd metal nanoparticle is 1%~70% in the catalyst, and partial size is 2~8nm.The present invention uses liquid phase reduction, and into certain density Pd salting liquid, ammonium hydroxide and NaOH is added, the complex ion aqueous slkali of Pd is made, then excessive reductant is added, under certain reaction temperature, directly restores the complex ion of Pd in scattered carbon black support.The Pd/C catalyst prepared by this method, in the HClO of the 0.1mol/L of oxygen saturation4There is excellent electro catalytic activity in solution.Solves Pd/C catalyst, Pd nano particle diameter is excessive, it is serious to reunite, it is difficult to the problem being prepared on a large scale.
Description
Technical field
The present invention relates to electrochemical techniques and fuel-cell catalyst fields, and in particular to a kind of uniform particle sizes, dispersion
Good, Pd/C catalyst that can be prepared on a large scale of property and preparation method thereof.
Background technique
In recent years, with the development of science and technology, the catalyst for possessing various performances and effect is constantly manufactured, wherein Pd
Base catalyst is wherein the most dazzling one kind.In many organic chemical reactions, such as Suzuki, Heck and Stille
Coupling etc. can use Pd nano particle as catalyst.Further, since people are essential to the urgent of the environmentally protective energy
It asks, application of the Pd nanocatalyst also made in terms of new energy is increasingly taken seriously.Wherein, Pd is in direct formic acid fuel electricity
Application in pond is a best illustration.Formic acid is with nontoxic, nonflammable, open-circuit voltage is high, Nafion membrane permeability is low
The features such as, in the great application prospect of fuel cell field.But general Pt/C catalyst has intermediate production when being catalyzed formic acid
Object CO is generated, so that Pt/C catalyst easily poisoning and deactivation, causes fuel cell efficiency to reduce, the service life shortens.And Pd/C is catalyzed
Agent then can effectively avoid the generation of above situation because Pd catalyst can by one-step method, directly by Oxidation of Formic Acid at
To the CO of catalyst nonhazardous effect2, other any intermediate products are not generated, and its catalytic activity is also than Pt high.This makes Pd
Catalyst has extraordinary application prospect in following low temperature liquid phase fuel cell field.
Currently, the method for prepare Pd/C catalyst both at home and abroad is mainly chemical reduction method, including gas-phase chemical reduction method with
Solution phase chemical reduction.Gas-phase chemical reduction method is the presoma salt of Pd to be attached on carbon, then by the methods of dipping
Under an atmosphere of hydrogen, the presoma of Pd is reduced to by Pd simple substance by high-temperature process.This method is although easy to operate, but due to needing
To pass through high-temperature process, so the Pd crystal grain formed is easy to the phenomenon that growing up, causing partial size and be unevenly distributed of reuniting, furthermore
Pd carrying capacity prepared by infusion process is generally less than 5%, is unsuitable for the preparation of big carrying capacity Pd/C catalyst.Solution phase chemical reduction is
It disperses the presoma salt and carbon dust of Pd in liquid phase, such as by reducing agent: formic acid, sodium borohydride, formaldehyde, ethyl alcohol, hydration
Hydrazine, citric acid etc., by Pd direct-reduction on carbon dust.But Pd nano particle was being prepared because of its special physicochemical properties
Easily there is phenomena such as excessive partial size and reunion, especially in the case where high load amount in Cheng Zhong.This just makes Pd/C catalyst phase
Pt/C catalyst is more difficult to prepare.For the generation for inhibiting Pd nano particle diameter excessive with agglomeration, prepared by people
It joined various Longer-chain surfactants and the polymer with weird atom donor and chemical group, such as CDTA in the process,
PVP, PVA, PAA etc., these additives are formed by way of strand package or Electrostatic Absorption in Pd nano grain surface
A protective layer, to prevent further growing up and reuniting for Pd nano particle.The addition of these surfactants and polymer,
Reduce the generation that Pd nano particle diameter is excessive and reunites really to a certain extent, but since these additives easily adsorb
It in Pd nano grain surface and is difficult to remove, so that the catalytic activity of catalyst and catalytic selectivity all significantly reduce, and urge
The electric conductivity of agent also declines therewith, this influences electrochemical catalysis very heavy.Although additive pair can be reduced by post-processing
The influence of Pd catalyst, but process is cumbersome, when consumption energy consumption, waste of resource is unfavorable for being prepared on a large scale for Pd catalyst.
The present invention provides a kind of simple process, energy conservation and environmental protection, the method that can be prepared on a large scale Pd/C catalyst, this method
Using solution phase chemical reduction, using ammonium hydroxide as complexing agent, Pd ion is set to be initially formed stable complex ion in the liquid phase, then again
By reducing agent, restore on carbon dust.The Pd/C catalyst prepared by this method, not only has pure free from admixture, and Pd is supported
The wide feature of modification scope, and its moderate in grain size are measured, well dispersed, performance is stablized.
Summary of the invention
While it is an object of the invention to solve above-mentioned technical problem, a kind of uniform particle sizes, good dispersion are provided
Pd/C catalyst, the catalyst have high catalytic activity and anti-decay property；It is a further object to provide
A kind of easy to operate, energy-saving and environment-friendly Pd/C method for preparing catalyst, and this method can be passed through and realize Pd/C catalyst
Be prepared on a large scale.
The purpose of the present invention is what is be achieved through the following technical solutions:
In a first aspect, the Pd/C catalyst is using carbon black as carrier, Pd metal the present invention provides a kind of Pd/C catalyst
Nano particle is dispersed on carbon black；In the catalyst mass percentage content of Pd metal nanoparticle be 1%~
70%, partial size is 2~8nm.
Preferably, the specific surface area of the carbon black is 500~1300m2/g；More preferable specific surface area is 750~1100m2/
g。
Preferably, the Pd metal nanoparticle partial size is 3~5nm.
Preferably, the mass percentage content of the Pd metal nanoparticle is 10%~30%.
Second aspect, the present invention provides a kind of preparation methods of Pd/C catalyst, the described method comprises the following steps:
A1, the source Pd presoma is dissolved in solvent, the water of ammonium hydroxide and certain volume is added, is formed under the conditions of magnetic agitation molten
Liquid A；
A certain amount of water, alkali and carbon black powders are added into solution A by A2, under the conditions of magnetic agitation, form liquid B；
A3, the liquid B is ultrasonically treated, then magnetic agitation under an inert atmosphere, reducing agent is then added；
A4, the liquid B after addition reducing agent is heated into reaction, then reaction product is filtered, wash, is dried in vacuo
Processing is to get Pd/C catalyst.
Preferably, in step A1, the source the Pd presoma is selected from PdCl2、Na2PdCl4、K2PdCl4, four ammino of dichloro
At least one of palladium, palladium acetate.
Preferably, in step A1, the molal volume concentration of Pd is 1.0 × 10 in the solution A-4~1.0 × 10-1mol/
L, preferred molar ratio are 5.0 × 10-3~5.0 × 10-2The excessive concentration of mol/L, Pd in the solution easily causes reunion, dense
Spend low be unfavorable in high volume；The molar ratio of the source Pd presoma and ammonium hydroxide is 1:10~50, and more preferable molar ratio is 1:15
~25.
Preferably, in step A2, molal volume concentration of the alkali in liquid B is 0~0.2mol/L, more preferably
0.1mol/L；The volume/mass of water and carbon black powders ratio is 1ml:0.1~30mg, and more preferable ratio is 1:1 (ml/mg).
Preferably, in step A3, the power of the ultrasonic treatment is 100W, ultrasonic time 30min；The magnetic agitation
Time is 2h；
The reducing agent is selected from NaBH4、KBH4, hydrazine hydrate, vitamin C, at least one of formaldehyde；The Pd with also
The molar ratio of former agent is 1:1~1000.Reducing agent dosage is very few, and Pd ion cannot be reduced completely in solution, leads to catalyst
The decline of Pd carrying capacity, yield reduce；Reducing agent dosage is excessive, on the one hand reducing agent is caused to waste, and Pd particle on the other hand can be made raw
Length is excessive, leads to partial size and is unevenly distributed.
Preferably, in step A3, the inert atmosphere is Ar (argon gas) or N2One or more of (nitrogen).
Preferably, in step A4, the heating reaction specifically: according to 2~7 DEG C/min of constant heating rate, will be added
Liquid B after reducing agent is heated to 20~90 DEG C, 0.5~6h of isothermal reaction；60 DEG C are more preferably heated to, isothermal reaction 2h.
Compared with prior art, the present invention have it is following the utility model has the advantages that
The present invention uses liquid phase reduction, into certain density Pd salting liquid, ammonium hydroxide and alkali is added, the complexing of Pd is made
Ion aqueous slkali, is then added excessive reductant, under certain reaction temperature, directly restores the complex ion of Pd scattered
Carbon black support on.The Pd/C catalyst prepared by this method, in the HClO of the 0.1mol/L of oxygen saturation4Have in solution
Excellent electro catalytic activity.Solve that Pd nano particle diameter in Pd/C catalyst is excessive, it is serious to reunite, it is difficult to be prepared on a large scale
Problem, Pd uniform particle sizes, good dispersion in the Pd/C catalyst of preparation have high catalytic activity and fade resistance
Energy；And preparation method of the invention is easy to operate, energy conservation and environmental protection is, it can be achieved that Pd/C catalyst is prepared on a large scale.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
Fig. 1 is the TEM picture of Pd/C catalyst prepared by the present invention.
Fig. 2 is the alcohol oxidation activity result of Pd/C catalyst prepared by embodiment 1；
Fig. 3 is the oxidation of ethanol fade resistance result of Pd/C catalyst prepared by embodiment 1.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, several changes and improvements can also be made.These belong to the present invention
Protection scope.
The basic step that Pd/C catalyst is prepared in following case study on implementation is as follows: firstly, according to prepared Pd/C catalyst
Pd content, weigh the source Pd presoma (PdCl2、Na2PdCl4、K2PdCl4, four ammino palladium of dichloro or palladium acetate) and carbon black powders
(specific surface area is 500~1300m2/g)；It is 1.0 × 10 that Pd salt, which is configured to molal volume concentration,-4~1.0 × 10-1Mol/L's
Pd salting liquid；Be added ammonium hydroxide into Pd salting liquid, form the complex ion of Pd and ammonia, be subsequently added into a certain amount of alkali (NaOH,
KOH), make the 0~0.2mol/L of molal volume concentration of alkali in the solution；Then, carbon black powder is added in Xiang Shangshu mixed solution
End, the ratio of water (ml) and carbon black (mg) are 1:0.1~30, the ultrasound 30min under 100W power；After ultrasound, in inertia
Reducing agent (NaBH is added in magnetic agitation 2h under atmosphere (argon gas or nitrogen)4、KBH4, hydrazine hydrate, vitamin C or formaldehyde；Pd with also
The molar ratio of former agent is 1:1~1000) stirring；Then above-mentioned mixed liquor is heated to according to 2~7 DEG C/min of constant heating rate
20~90 DEG C, Pd/C catalyst can be obtained after 0.5~6h of isothermal reaction.
Case study on implementation 1
1,0.1185mmol PdCl is weighed2In flask, the H that HCl is configured to 0.1M is added2PdCl4Then solution is added
5ml water, uniformly rear addition 400ul ammonium hydroxide to be mixed, magnetic agitation to solution is at colorless and transparent state；Pd's rubs in the solution
Your volumetric concentration is 1.8 × 10-2The molar ratio of mol/L, Pd and ammonium hydroxide is 1:22；
2,30ml ultrapure water is added into flask, the NaOH solution 1.5ml, magnetic agitation 20min of 1M is then added；
3,37.5mg carbon black powders are added into flask, ultrasound 30min, is then transferred to oil for flask under 100W power
In bath, under Ar gas atmosphere, magnetic agitation 2h；
4,1ml formalin then under the conditions of magnetic agitation, is added into flask, stirs 10min；Pd and formaldehyde rub
You are than being 1:115.5；
5, above-mentioned mixed liquor is heated to 60 DEG C with the rate of heat addition of 2 DEG C/min, and isothermal reaction 2h at this temperature；
6, obtained reaction product is filtered, and with milli-Q water 4 times, 80 DEG C of dryings in a vacuum drying oven
4h is to get Pd/C catalyst is arrived, as shown in Figure 1, good dispersion of the Pd in carbon black, uniform particle sizes.Through detection gained catalyst
The mass content of middle Pd is that 25%, Pd partial size is 5nm or so.
Case study on implementation 2
1,0.1185mmol Na is weighed2PdCl4In flask, the Na that ultrapure water is configured to 0.1M is added2PdCl4Solution,
Then be added 5ml water, it is to be mixed uniformly after, be added 400ul ammonium hydroxide, magnetic agitation to solution is at colorless and transparent state；It is described molten
The molal volume concentration of Pd is 1.8 × 10 in liquid-2The molar ratio of mol/L, Pd and ammonium hydroxide is 1:22；
2,30ml ultrapure water is added into flask, the NaOH solution 1.5ml, magnetic agitation 20min of 1M is then added；
3,37.5mg carbon black powders are added into flask, ultrasound 30min, is then transferred to oil for flask under 100W power
In bath, under Ar gas atmosphere, magnetic agitation 2h；
4,1ml formalin then under the conditions of magnetic agitation, is added into flask, stirs 10min；Pd and formaldehyde rub
You are than being 1:115.5；
5, above-mentioned mixed liquor is heated to 60 DEG C with the rate of heat addition of 2 DEG C/min, and isothermal reaction 2h at this temperature；
6, obtained reaction product is filtered, and with milli-Q water 4 times, 80 DEG C of dryings in a vacuum drying oven
4h obtains Pd/C catalyst, good dispersion of the Pd in carbon black, uniform particle sizes.Quality through Pd in detection gained catalyst contains
It is 5nm or so that amount, which is 25%, Pd partial size,.
Case study on implementation 3
1,0.1185mmol K is weighed2PdCl4In flask, the K that ultrapure water is configured to 0.1M is added2PdCl4Solution, so
Afterwards be added 5ml water, it is to be mixed uniformly after, be added 400ul ammonium hydroxide, magnetic agitation to solution is at colorless and transparent state；The solution
The molal volume concentration of middle Pd is 1.8 × 10-2The molar ratio of mol/L, Pd and ammonium hydroxide is 1:22；
2,30ml ultrapure water is added into flask, the NaOH solution 1.5ml, magnetic agitation 20min of 1M is then added；
3,37.5mg carbon black powders are added into flask, ultrasound 30min, is then transferred to oil for flask under 100W power
In bath, under Ar gas atmosphere, magnetic agitation 2h；
4,1ml formalin then under the conditions of magnetic agitation, is added into flask, stirs 10min；Pd and formaldehyde rub
You are than being 1:115.5；
5, above-mentioned mixed liquor is heated to 60 DEG C with the rate of heat addition of 2 DEG C/min, and isothermal reaction 2h at this temperature；
6, obtained reaction product is filtered, and with milli-Q water 4 times, 80 DEG C of dryings in a vacuum drying oven
4h obtains Pd/C catalyst, good dispersion of the Pd in carbon black, uniform particle sizes.Quality through Pd in detection gained catalyst contains
It is 5nm or so that amount, which is 25%, Pd partial size,.
Case study on implementation 4
1,0.1185mmol Na is weighed2PdCl4In flask, the Na that ultrapure water is configured to 0.1M is added2PdCl4Solution,
Then be added 5ml water, it is to be mixed uniformly after, be added 400ul ammonium hydroxide, magnetic agitation to solution is at colorless and transparent state；It is described molten
The molal volume concentration of Pd is 1.8 × 10 in liquid-2The molar ratio of mol/L, Pd and ammonium hydroxide is 1:22；
2,30ml ultrapure water is added into flask, the NaOH solution 1.5ml, magnetic agitation 20min of 1M is then added；
3,37.5mg carbon black powders are added into flask, ultrasound 120min, is then transferred to oil for flask under 50W power
In bath, under Ar gas atmosphere, magnetic agitation 1h.
4,10ml 0.1M KBH then under the conditions of magnetic agitation, is added into flask4Solution stirs 10min；Pd with
KBH4Molar ratio be 1:8.4；
5, above-mentioned mixed liquor is heated to 20 DEG C with the rate of heat addition of 4 DEG C/min, and isothermal reaction 6h at this temperature；
6, obtained reaction product is filtered, and with milli-Q water 4 times, 80 DEG C of dryings in a vacuum drying oven
4h obtains Pd/C catalyst, good dispersion of the Pd in carbon black, uniform particle sizes.Quality through Pd in detection gained catalyst contains
It is 4nm or so that amount, which is 25%, Pd partial size,.
Case study on implementation 5
1,0.6mmol Na is weighed2PdCl4In flask, the Na that ultrapure water is configured to 0.1M is added2PdCl4Solution, then
Be added 25ml water, it is to be mixed uniformly after, be added 2ml ammonium hydroxide, magnetic agitation to solution is at colorless and transparent state；Pd in the solution
Molal volume concentration be 1.8 × 10-2The molar ratio of mol/L, Pd and ammonium hydroxide is 1:21.7；
2,150ml ultrapure water is added into flask, the NaOH solution 7.5ml, magnetic agitation 20min of 1M is then added；
3,187.5mg carbon black powders are added into flask, ultrasound 5min, is then transferred to oil for flask under 150W power
In bath, under Ar gas atmosphere, magnetic agitation 4h；
4,5ml formalin then under the conditions of magnetic agitation, is added into flask, stirs 10min；Pd and formaldehyde rub
You are than being 1:114；
5, above-mentioned mixed liquor is heated to 90 DEG C with the rate of heat addition of 7 DEG C/min, and isothermal reaction at this temperature
0.5h；
6, obtained reaction product is filtered, and with milli-Q water 4 times, 80 DEG C of dryings in a vacuum drying oven
4h obtains Pd/C catalyst, good dispersion of the Pd in carbon black, uniform particle sizes.Quality through Pd in detection gained catalyst contains
It is 5nm or so that amount, which is 25%, Pd partial size,.
Compliance test result:
Pd/C catalyst prepared by case study on implementation 1 carries out catalytic activity and fade resistance test, and test method is as follows:
Oxidation of ethanol (EOR) active testing: preparation is loaded with the platinum carbon electrode of the Pd/C catalyst of the synthesis of embodiment 1, air
In done in the ethyl alcohol of 1M and the NaOH solution of 1M cyclic voltammetric (CV) test, sweep speed be 50mV/s.
The test of oxidation of ethanol fade resistance: chronoamperometry (CA) is done in the NaOH solution of the ethyl alcohol of 1M and 1M in air
Test, current potential are the spike potential in corresponding active testing CV.
Test result is as shown in Figures 2 and 3.Fig. 2 and Fig. 3's the results show that the embodiment of the present invention preparation Pd/C catalyst
Have good catalytic activity and fade resistance.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make a variety of changes or modify within the scope of the claims, this not shadow
Ring substantive content of the invention.In the absence of conflict, the feature in embodiments herein and embodiment can any phase
Mutually combination.
Claims (10)
1. a kind of Pd/C catalyst, which is characterized in that for the Pd/C catalyst using carbon black as carrier, Pd metal nanoparticle is uniform
It is dispersed on carbon black；In the catalyst mass percentage content of Pd metal nanoparticle be 1%~70%, partial size be 2~
8nm。
2. Pd/C catalyst according to claim 1, which is characterized in that the specific surface area of the carbon black be 500~
1300m2/g。
3. Pd/C catalyst according to claim 1, which is characterized in that the Pd metal nanoparticle partial size is 3~5nm.
4. Pd/C catalyst according to claim 1, which is characterized in that the mass percent of the Pd metal nanoparticle contains
Amount is 10%~30%.
5. a kind of preparation method of Pd/C catalyst as described in any one of claims 1 to 4, which is characterized in that the side
Method the following steps are included:
A1, the source Pd presoma is dissolved in solvent, the water of ammonium hydroxide and certain volume is added, forms solution A under the conditions of magnetic agitation；
A certain amount of water, alkali and carbon black powders are added into solution A by A2, under the conditions of magnetic agitation, form liquid B；
A3, the liquid B is ultrasonically treated, then magnetic agitation under an inert atmosphere, reducing agent stirring is then added；
A4, the liquid B after addition reducing agent is heated into reaction, then reaction product is filtered, is washed, at vacuum drying
Reason is to get Pd/C catalyst.
6. the preparation method of Pd/C catalyst according to claim 5, which is characterized in that in step A1, the source Pd
Presoma is selected from PdCl2、Na2PdCl4、K2PdCl4, four ammino palladium of dichloro, at least one of palladium acetate.
7. the preparation method of Pd/C catalyst according to claim 5, which is characterized in that in step A1, in the solution A
The molal volume concentration of Pd is 1.0 × 10-4~1.0 × 10-1mol/L；The molar ratio of the Pd and ammonium hydroxide is 1:10~50.
8. the preparation method of Pd/C catalyst according to claim 5, it is characterised in that in step A2, the alkali is
At least one of NaOH, KOH, the molal volume concentration in liquid B are 0~0.2mol/L, the body of water and carbon black powders
Product/mass ratio is 1ml:0.1~30mg.
9. the preparation method of Pd/C catalyst according to claim 5, which is characterized in that in step A3, at the ultrasound
The power of reason is 50~150W, and ultrasonic time is 5~120min；The magnetic agitation time is 0~240min.
The reducing agent is selected from NaBH4、KBH4, hydrazine hydrate, vitamin C, at least one of formaldehyde；The Pd and reducing agent
Molar ratio be 1:1~1000.
10. the preparation method of Pd/C catalyst according to claim 5, which is characterized in that in step A4, the heating is anti-
It answers specifically: according to 2~7 DEG C/min of constant heating rate, the liquid B after addition reducing agent is heated to 20~90 DEG C, constant temperature
React 0.5~6h.
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| CN110586081A (en) * | 2019-09-09 | 2019-12-20 | 浙江新和成股份有限公司 | Palladium-carbon catalyst and preparation method and application thereof |
| CN112064056A (en) * | 2020-08-27 | 2020-12-11 | 西南民族大学 | Method for economically and efficiently electrochemically and organically synthesizing biphenyl substances |
| CN113845544A (en) * | 2021-10-29 | 2021-12-28 | 西安凯立新材料股份有限公司 | Preparation method of organometallic compound [1, 3-bis (diphenylphosphino) propane ] palladium (II) chloride |
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