CN107233917B - Preparation of palladium-hydrogen nano-particles and application of palladium-hydrogen nano-particles in electrocatalytic oxidation of formic acid - Google Patents
Preparation of palladium-hydrogen nano-particles and application of palladium-hydrogen nano-particles in electrocatalytic oxidation of formic acid Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 38
- 239000001257 hydrogen Substances 0.000 title claims abstract description 37
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 27
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 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 12
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 12
- 230000003647 oxidation Effects 0.000 title claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 65
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000853 adhesive Substances 0.000 claims abstract description 3
- 230000001070 adhesive effect Effects 0.000 claims abstract description 3
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 5
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical group 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 19
- 238000005119 centrifugation Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000001276 controlling effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000011943 nanocatalyst Substances 0.000 abstract description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000000634 powder X-ray diffraction Methods 0.000 description 8
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- -1 palladium hydride Chemical class 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/121—Metal hydrides
-
- B01J35/40—
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- B01J35/50—
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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
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
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- H—ELECTRICITY
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- 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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
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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
- H01M4/9091—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
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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
- H01M4/928—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- 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
Abstract
Preparation of palladium-hydrogen nano particles and application thereof in electrocatalytic oxidation of formic acid relate to palladium-hydrogen nano catalytic materials. Mixing the Pd nanoparticles with a solvent in a reaction vessel; heating the reaction container, cooling, collecting the product, cleaning the sample with ethanol to remove the surface adhesive, vacuum drying, and controlling the reaction temperature to obtain PdHxThe preparation method is simple, the reaction conditions are mild, stable palladium hydrogen can be directly formed after the palladium nano particles are subjected to heat treatment, the β phase palladium hydrogen catalyst can be cleaned by ethanol centrifugation or ozone ultraviolet cleaning, and the palladium hydrogen nano catalysts with different H ratios can be obtained by regulating and controlling the reaction temperature.
Description
Technical Field
The invention relates to a palladium-hydrogen nano catalytic material, in particular to a preparation method of palladium-hydrogen nano particles and application of the palladium-hydrogen nano particles in electrocatalytic oxidation of formic acid.
Background
Palladium (Pd) is a very important noble metal catalyst and has wide application in many fields. In particular, Pd has extremely strong adsorption capacity to H2, forms a unique PdH compound, and shows excellent properties in aspects of hydrogen storage, sensing, hydrogen purification and the like (Adams Brian D., Chen Aicheng. the role of palladium in hydrogen economy. materials Today,2011,14(6): 282-289). The synthesis of PdH compounds by exposure of Pd to an atmosphere of H2, or by giving negative potentials in electrochemical systems has been the conventional method of synthesizing PdH compounds in the past (Li G., Kobayashi H., Dekura S., Ikeda R., Kubota Y., Kato K., Takata M., Yamamoto T., Matsumura S., Kitagawa H.shape-dependent hydrogen-crystal precursors in Pd nanocrystals: Which diodes hydrofront, octahedron (111) or cube (100) J Am ChemsElectroc, 2014,136(29): 10222. sub.25; Zalineva A., Baranton S., Coutane C., Jeerwincz. Kiectrochero of microwave of 201525), and finally the synthesis of these compounds has become slow stabilized by Laugh H1605, Which was not stabilized by Layak 1605. Recent studies have found that in reactions in which hydrogen is involved in Pd nanoparticles as a catalyst, such as organic catalytic hydrogenation, electrocatalytic reduction of carbon dioxide, etc. (Min X., Kanan M.W. Pd-catalyzed hydrogenation of carbon dioxide to form: High mass activity at low over-atmospheric and identification of the deactivation pathway J Am ChemSoc,2015,137(14): 4701-4708; Kim Seok Kim cheghee, Lee Ji Hoon, Kim JaeUnjun, LeeHyunjoo, Moon Sangg Heup.146 for use of shape-controlled Pd nanoparticles in-situ selection of Catalysis of hydrolysis. journal of Catalysis,2013,306: H) can play an important role in the in-situ catalytic activity of in-situ hydrogenation of Catalysis, such as H, in particular for the in-situ catalytic hydrogenation of Catalysis. Unfortunately, these in situ generated PdH are not stable enough and the ratio of Pd to H cannot be adjusted, thus limiting their wider application. Therefore, the PdHx with stable control synthesis and adjustable proportion has important significance.
Disclosure of Invention
The invention aims to provide preparation of palladium-hydrogen nanoparticles and application of the palladium-hydrogen nanoparticles in electrocatalytic oxidation of formic acid.
The preparation method of the palladium-hydrogen nano-particles comprises the following steps:
1) mixing the Pd nanoparticles with a solvent in a reaction vessel;
in the step 1), the reaction vessel can adopt a reaction kettle and the like; the ratio of the Pd nanoparticles to the solvent can be 5 mg: 10mL, wherein the Pd nanoparticles are calculated according to the mass ratio, and the solvent is calculated according to the volume ratio; the solvent can be selected from alcohols or amines, the alcohols can be selected from one of methanol, ethanol and the like, and the amines can be selected from one of n-butylamine, n-hexylamine and the like.
2) Heating the reaction container, cooling, collecting the product, cleaning the sample with ethanol to remove the surface adhesive, vacuum drying, and controlling the reaction temperature to obtain PdHxA compound is provided.
In the step 2), the heating temperature can be 80 ℃, and the heating time can be 6 hours; when the reaction temperature is more than 150 ℃, the ratio of H to Pd is 0.43; when the reaction temperature is 130 ℃, the ratio of H to Pd is 0.33; when the reaction temperature is 100 ℃, the ratio of H to Pd is 0.29; when the reaction temperature was 80 ℃, the ratio of H to Pd was 0.10.
The palladium-hydrogen nano-particles are applied to the electrocatalytic oxidation of formic acid, beta-phase palladium-hydrogen catalysts can be adopted for the palladium-hydrogen nano-particles, and the beta-phase palladium-hydrogen catalysts can be applied to fuel cells.
The palladium-hydrogen nano catalyst or commercial Pd black catalyst prepared by the method provided by the invention is mixed with absolute ethyl alcohol, then the mixture is dripped on a working electrode and is placed in a mixed solution containing 0.25M formic acid and 0.5M sulfuric acid, wherein a Pt wire is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and scanning is carried out at room temperature between-0.25V and 0.60V (scanning speed: 50mV/s) by a cyclic voltammetry method.
The invention has the following outstanding advantages:
1) the preparation method is simple, the reaction condition is mild, and stable palladium hydrogen can be directly formed after the palladium nano particles are subjected to heat treatment.
2) The beta-phase palladium-hydrogen catalyst obtained by the method provided by the invention can obtain a clean surface through ethanol centrifugal cleaning or ozone ultraviolet cleaning.
3) The method provided by the invention can obtain the palladium-hydrogen nano-catalysts with different H ratios by regulating and controlling the reaction temperature.
4) The invention is suitable for large-scale preparation.
5) The beta-phase palladium-hydrogen catalyst obtained by the method provided by the invention has excellent catalytic activity on the electro-catalytic oxidation of formic acid, not only effectively improves the catalytic activity, but also effectively reduces the oxidation overpotential.
Drawings
FIG. 1 shows β -PdH prepared from n-butylamine in example 1 of the present invention0.43X-ray powder diffractogram of catalyst sample.
FIG. 2 shows different ratios of n-butylamine as a solution prepared at different reaction temperatures in examples 2 to 5 of the present inventionExample β PdHxX-ray powder diffraction pattern of nanocrystalline catalyst samples.
FIG. 3 shows β -PdH prepared from butylamine in example 1 of the present invention0.43The nanocrystalline catalyst sample is placed for 12 months at room temperature and then is mixed with freshly prepared β -PdH0.43X-ray powder diffraction pattern contrast of nanocrystalline catalyst.
FIG. 4 shows β -PdH prepared from butylamine in example 1 of the present invention0.43And (3) comparing X-ray powder diffraction patterns of nanocrystalline catalyst samples calcined for 2 hours at different temperatures in an argon atmosphere.
FIG. 5 shows β -PdH prepared from butylamine in example 1 of the present invention0.43Comparison of cyclic voltammetry of nanocrystalline catalyst samples with commercial Pd black in electrocatalytic oxidation of formic acid. The test conditions were: and (2) scanning a mixed solution of 0.25M formic acid and 0.5M sulfuric acid, wherein a Pt filament is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, a glassy carbon electrode loaded with a catalyst is used as a working electrode at a voltage interval of-0.25-0.60V at room temperature by a cyclic voltammetry (scanning speed: 50 mV/s).
Detailed Description
The following examples will further illustrate the present invention with reference to the accompanying drawings.
Example 1
5mg of commercial Pd black and 10mL of n-butylamine are uniformly mixed in a 25mL reaction kettle, then the reaction kettle filled with the reaction liquid is placed in an oven, the temperature is raised to 150 ℃ from the room temperature and is kept constant for 5.0h, and then the temperature is naturally reduced to the room temperature. Finally, all the products were collected by centrifugation and the samples were washed several times with ethanol to remove the surface adhesion agents. The phase analysis of the compound is beta-phase palladium hydride, which belongs to a face-centered cubic structure, and the X-ray powder diffraction is shown in figures 1 and 3-5.
Example 2
5mg of commercial Pd black and 10mL of n-butylamine are uniformly mixed in a 25mL reaction kettle, then the reaction kettle filled with the reaction liquid is placed in an oven, the temperature is raised to 220 ℃ from the room temperature and is kept constant for 5.0h, and then the temperature is naturally reduced to the room temperature. Finally, all the products were collected by centrifugation and the samples were washed several times with ethanol to remove the surface adhesion agents. The phase analysis was the same as in example 1, and the corresponding X-ray powder diffraction pattern is shown in FIG. 2.
Example 3
5mg of commercial Pd black and 10mL of n-butylamine are uniformly mixed in a 25mL reaction kettle, then the reaction kettle filled with the reaction liquid is placed in an oven, the temperature is raised to 130 ℃ from the room temperature and is kept constant for 5.0h, and then the temperature is naturally reduced to the room temperature. Finally, all the products were collected by centrifugation and the samples were washed several times with ethanol to remove the surface adhesion agents. The phase analysis was the same as in example 1, and the ratio of H to Pd in the palladium hydride sample was 0.33. The corresponding X-ray powder diffraction is shown in figure 2.
Example 4
5mg of commercial Pd black and 10mL of n-butylamine are uniformly mixed in a 25mL reaction kettle, then the reaction kettle filled with the reaction liquid is placed in an oven, the temperature is raised to 100 ℃ from the room temperature and is kept constant for 5.0h, and then the temperature is naturally lowered to the room temperature. Finally, all the products were collected by centrifugation and the samples were washed several times with ethanol to remove the surface adhesion agents. The phase analysis was the same as in example 1, and the ratio of H to Pd in the palladium hydride sample was 0.29. The corresponding X-ray powder diffraction is shown in figure 2.
Example 5
5mg of commercial Pd black and 10mL of n-butylamine are uniformly mixed in a 25mL reaction kettle, then the reaction kettle filled with the reaction liquid is placed in an oven, the temperature is raised to 80 ℃ from the room temperature and is kept constant for 5.0h, and then the temperature is naturally lowered to the room temperature. Finally, all the products were collected by centrifugation and the samples were washed several times with ethanol to remove the surface adhesion agents. The phase analysis was the same as in example 1, and the ratio of H to Pd in the palladium hydride sample was 0.10. The corresponding X-ray powder diffraction is shown in figure 2.
Example 6
5mg of commercial Pd black and 10mL of methanol are uniformly mixed in a 25mL reaction kettle, then the reaction kettle filled with the reaction liquid is placed in an oven, the temperature is raised to 220 ℃ from the room temperature and is kept constant for 5.0h, and then the temperature is naturally reduced to the room temperature. Finally, all the products were collected by centrifugation and the samples were washed several times with ethanol to remove the surface adhesion agents. The phase analysis was the same as in example 1, and the ratio of H to Pd in the palladium hydride sample was 0.43.
Example 7
Mixing 5mg of commercial Pd black and 10mL of ethanol uniformly in a 25mL reaction kettle, then putting the reaction kettle filled with the reaction solution into an oven, heating to 220 ℃ from room temperature, keeping the temperature for 5.0h, and then naturally cooling to room temperature. Finally, all the products were collected by centrifugation and the samples were washed several times with ethanol to remove the surface adhesion agents. The phase analysis was the same as in example 1, and the ratio of H to Pd in the palladium hydride sample was 0.43.
Example 8
Uniformly mixing 5mg of commercial Pd black and 10mL of n-hexylamine in a 25mL reaction kettle, then putting the reaction kettle filled with the reaction liquid into an oven, heating to 220 ℃ from room temperature, keeping the temperature for 5.0h, and then naturally cooling to room temperature. Finally, all the products were collected by centrifugation and the samples were washed several times with ethanol to remove the surface adhesion agents. The phase analysis was the same as in example 1, and the ratio of H to Pd in the palladium hydride sample was 0.43.
The invention discloses a preparation method of beta-phase palladium-hydrogen nano particles with adjustable and stable hydrogen content, which is characterized in that low-boiling-point alcohols or amine solvents (such as methanol, ethanol, n-butylamine, n-hexylamine and the like) are adopted, and a palladium catalyst is heated to obtain palladium-hydrogen nano crystals. The beta-phase palladium-hydrogen nanocrystalline catalysts with different proportions can be obtained by adjusting the reaction temperature. Compared with other synthesized palladium-hydrogen nanocrystalline catalysts, the method has the advantages of simple operation and controllable process, and the obtained beta-phase palladium-hydrogen catalyst has adjustable and stable composition proportion. In the electrocatalytic oxidation of formic acid, not only is the catalytic activity high, but also the oxidation overpotential is extremely low. Has wide application prospect in the aspects of fuel cells, organic catalytic hydrogenation and the like.
Claims (4)
1. A preparation method of palladium-hydrogen nanoparticles is characterized by comprising the following steps:
1) mixing the Pd nanoparticles with a solvent in a reaction vessel; the ratio of the Pd nanoparticles to the solvent is 5 mg: 10mL, wherein the Pd nanoparticles are calculated according to the mass ratio, and the solvent is calculated according to the volume ratio; the solvent is selected from alcohols or amines; the alcohol is selected from one of methanol and ethanol, and the amine is selected from one of n-butylamine and n-hexylamine;
2) heating the reaction container, cooling, collecting the product, cleaning the sample with ethanol to remove the adhesive on the surface, and vacuum drying to obtain PdHxA compound; when the reaction temperature is more than 150 ℃, the ratio of H to Pd is 0.43; when the reaction temperature is 130 ℃, the ratio of H to Pd is 0.33; when the reaction temperature is 100 ℃, the ratio of H to Pd is 0.29; when the reaction temperature was 80 ℃, the ratio of H to Pd was 0.10.
2. The method of claim 1, wherein in step 1), the reaction vessel is a reaction vessel.
3. Use of palladium hydrogen nanoparticles prepared by the method of claim 1 in the electrocatalytic oxidation of formic acid.
4. The use according to claim 3, wherein the palladium-hydrogen nanoparticles are used in fuel cells.
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| CN103894232A (en) * | 2014-04-10 | 2014-07-02 | 中国科学院福建物质结构研究所 | Catalyst for synthesizing methyl formate by formylating methyl nitrite, preparation method and application of catalyst |
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| CN103894232A (en) * | 2014-04-10 | 2014-07-02 | 中国科学院福建物质结构研究所 | Catalyst for synthesizing methyl formate by formylating methyl nitrite, preparation method and application of catalyst |
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| Title |
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| Synthesis of Stable Shape-Controlled Catalytically Active β‑Palladium Hydride;Zipeng Zhao et al.;《J. Am. Chem. Soc.》;20151204;第137卷;第15672-15675页及supporting information S1-S13页 * |
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