CN111659386A - Platinum-based catalyst containing lanthanide element simple substance or compound - Google Patents

Platinum-based catalyst containing lanthanide element simple substance or compound Download PDF

Info

Publication number
CN111659386A
CN111659386A CN202010435137.5A CN202010435137A CN111659386A CN 111659386 A CN111659386 A CN 111659386A CN 202010435137 A CN202010435137 A CN 202010435137A CN 111659386 A CN111659386 A CN 111659386A
Authority
CN
China
Prior art keywords
solution
platinum
based catalyst
catalyst
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010435137.5A
Other languages
Chinese (zh)
Inventor
王玲钰
欧阳应根
肖松涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Institute of Atomic of Energy
Original Assignee
China Institute of Atomic of Energy
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Institute of Atomic of Energy filed Critical China Institute of Atomic of Energy
Priority to CN202010435137.5A priority Critical patent/CN111659386A/en
Publication of CN111659386A publication Critical patent/CN111659386A/en
Pending legal-status Critical Current

Links

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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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
    • 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
    • H01M4/9041—Metals or alloys
    • 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
    • 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
    • H01M4/923—Compounds thereof with non-metallic elements
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention belongs to the technical field of catalysts, and relates to a platinum-based catalyst containing a lanthanide element simple substance or compound. The platinum-based catalyst comprises a catalytic active substance and a catalytic auxiliary substance, wherein the catalytic active substance comprises metal platinum, the catalytic auxiliary substance comprises a cocatalyst, and the cocatalyst comprises one or more of elementary substances or compounds of lanthanide monoisotope cerium-144, samarium-151, gadolinium-153 or terbium-157. The platinum-based catalyst containing the lanthanide element simple substance or the compound has better catalytic performance and stability.

Description

Platinum-based catalyst containing lanthanide element simple substance or compound
Technical Field
The invention belongs to the technical field of catalysts, and relates to a platinum-based catalyst containing a lanthanide element simple substance or compound.
Background
Catalyst materials and catalytic technology are one of the fundamental and critical materials and technologies for the development of the chemical industry today. In modern industry, the production value produced by catalytic technology accounts for about 30% of the total value of national economy.
The electronic arrangement of the Pt outer layer of the noble metal is 5d86s2And the second outer layer has 8 d electrons, and the track is not filled. And because the energy level contains unpaired electrons, Pt can show stronger ferromagnetism or paramagnetism in physical properties; in the chemical adsorption process, these d electrons of Pt can pair with p electrons or s electrons in the adsorbate, and chemical adsorption occurs to generate an intermediate product, thereby activating the adsorbed molecules.
In modern industry, platinum catalysts are mainly used in inorganic chemical industry, petroleum refining, organic chemical industry, C1 chemical industry, fine chemical industry, purification and treatment of automobile exhaust and industrial gas, and the fields of fuel cells, sensors and the like, so that the platinum catalysts have very important positions in the aspects of industrial catalysis, environmental protection and green energy technology and show wide application prospects.
However, pure Pt as a catalyst has 3 major disadvantages, namely low utilization, low poisoning resistance, and high price. In response to these disadvantages, much research worldwide has been devoted to the development of highly active platinum catalysts and the reduction of the amount of platinum catalyst used in order to improve the catalytic activity, selectivity, and life span of the Pt catalyst.
With respect to Pt catalysts, the main current research directions are:
1. unitary Pt-based catalyst
The research direction of the unitary Pt-based catalyst focuses on finding a catalyst carrier with excellent performance and changing the size and surface state of Pt particles. For example, Zhu and the like adopt functionalized multi-wall carbon nanotubes dispersed in polyaniline as a carrier to synthesize a catalyst with good Pt/MWCNT/PAN dispersibility. Research results show that compared with a catalyst taking pure polyaniline as a carrier, the catalyst has higher catalytic activity. For example, Wu and the like are used for preparing a nano carbon material with a shell-core structure, carbon black particles are used as a core for loading, a graphite layer doped with carbon black is used as a shell, and the catalyst has high catalytic activity. For another example, Zhang and the like prepare the nanoflower with novel appearance through a template-free electrodeposition method, and the nanoflower has porous appearance and can provide larger active centers.
2. Binary Pt-based catalyst
The alloy type catalyst prepared by adding the second metal which is easy to adsorb oxygen-containing substances into the pure Pt catalyst can improve the poisoning resistance of the catalyst, thereby greatly improving the performance of the catalyst. The Pt-based binary catalysts which are researched more and have better catalytic effect at present comprise PtRu, PtPd, PtSn, PtAu, PtNi, PtCo and metal oxide (Pt + MO)xAnd wherein M ═ Ti, W, Zr, Ce, Ta), and the like.
3. Multi-element Pt-based catalyst
Researchers have attempted to improve Pt-based alloys by adding third and even fourth metals to increase their catalytic activity. For example, Park et al have studied the electronic and chemical effects of Pt/Ni, Pt/Ru/Ni nanocatalysts in the oxidation process of methanol. As another example, Jeon et al synthesized a PtCoCr three-way catalyst, and the experimental results showed that Pt30Co30Cr40The catalyst has good electro-oxidation property, stability and catalytic effect on methanol, and is an excellent methanol electro-oxidation catalyst.
In summary, although scientists have performed several works in the field of noble metal Pt catalysis, the different methods are superior and inferior. And the industrial application of these Pt catalytic materials still faces many challenges, such as large-scale controllable synthesis method, catalytic material stability, precise regulation of metal loading, catalyst poisoning resistance, how to better combine the advanced preparation method of metal materials with carbon loading materials, and the like. Therefore, new ideas for noble metal Pt catalysis are under way.
Disclosure of Invention
The invention aims to provide a platinum-based catalyst containing a lanthanide element simple substance or compound, so as to have better catalytic performance and stability.
To achieve this object, in a basic embodiment, the present invention provides a platinum-based catalyst comprising a lanthanide element or compound, said platinum-based catalyst comprising a catalytically active species comprising metallic platinum and a catalytic auxiliary species comprising a promoter, said promoter comprising one or more of the lanthanide monoisotopes cerium-144, samarium-151, gadolinium-153 or terbium-157 (said platinum-based catalyst being useful in fuel cells).
In a preferred embodiment, the present invention provides a platinum-based catalyst containing a lanthanide element or a compound thereof, wherein the mass ratio of the catalytically active material to the catalytic auxiliary material is 1:0.01 to 10.
In a preferred embodiment, the present invention provides a platinum-based catalyst comprising a lanthanide element or compound, wherein the mass ratio of the catalytically active species to the promoter is from 1:0.0001 to 1.
In a preferred embodiment, the invention provides a platinum-based catalyst containing a lanthanide element or compound, wherein the promoter further comprises one or more selected from gold, silver, cobalt, nickel, palladium, ruthenium, tin, bismuth, copper, iron, iridium, manganese, molybdenum, rhodium, tungsten, and zinc.
In a preferred embodiment, the invention provides a platinum-based catalyst containing a lanthanide element or compound, wherein the catalytic auxiliary substance further comprises a catalyst carrier selected from one or more of activated carbon, silicon carbide, aluminum oxide, graphene, silicon dioxide and zeolite.
In a preferred embodiment, the present invention provides a platinum-based catalyst comprising a lanthanide element or a compound, wherein said compound is an inorganic compound or an organic compound.
In a preferred embodiment, the present invention provides a platinum-based catalyst comprising a lanthanide element or a compound, wherein said compound is an oxide.
The platinum-based catalyst containing the lanthanide element or the compound has the beneficial effects of better catalytic performance and stability.
Detailed Description
The following examples further illustrate specific embodiments of the present invention.
Example 1: preparation examples
By using the principle of isotope separation method, the CeO with natural isotope abundance is separated by a CAE-1 type magnetic separation device of nuclear institute of atomic energy science of China2The concrete operating conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameter Ce-144-100. Collecting the separated CeO at the discharge port2The abundance of Ce-144 was 100% by ICP-MS, thereby obtaining144CeO2(prepared analogously to the following examples)144CeO2)。
0.6g of Vulcan XC-72 carbon powder and 0.1g of carbon powder are taken144CeO2Powder, 10.25mL of H2PtCl6(0.1mol/L) solution and 17.04mL of NiSO4(0.1mol/L) solution is mixed and added into 80mL deionized water, ultrasonic treatment is carried out for 30min to lead the solution to be dispersed evenly, then under stirring, 1mol/L NaOH solution is used for adjusting the pH value to 8-9, and excessive NaBH of 2.0mg/mL is slowly added4The solution was stirred for 3 h. Washing with ultrapure water until no Cl is formed-Then vacuum drying at 60 ℃ for 4h to obtain Pt-Ni-144CeO2a/C catalyst.
Example 2: comparative preparation example
0.6g of Vulcan XC-72 carbon powder and 10.25mL of H are taken2PtCl6(0.1mol/L) solution and 17.04mL of NiSO4(0.1mol/L) solution is mixed and added into 80mL deionized water, ultrasonic treatment is carried out for 30min to lead the solution to be dispersed evenly, then under stirring, 1mol/L NaOH solution is used for adjusting the pH value to 8-9, and excessive NaBH of 2.0mg/mL is slowly added4The solution was stirred for 3 h. Washing with ultrapure water until no Cl is formed-And then, drying for 4 hours in vacuum at the temperature of 60 ℃ to obtain the Pt-Ni/C catalyst.
Example 3: preparation examples
0.6g of Vulcan XC-72 carbon powder and 0.1g of carbon powder are taken144CeO2The powder is added into a 250mL beaker together with 80mL of ethylene glycol, ultrasonically shaken for 2H, and 10.25mL of H is added dropwise2PtCl6(0.1mol/L) solution and 16.97mL of CoCl2(0.1mol/L) solution, adding 21mL formic acid, stirring at room temperature for 30min, placing in microwave oven, heating for 20s, repeating for 5 times, heating for 10s, repeating for 5 times, cooling, vacuum filtering, and vacuum dryingObtaining Pt-Co-144CeO2a/C catalyst.
Example 4: comparative preparation example
0.6g of Vulcan XC-72 carbon powder and 80mL of ethylene glycol are added into a 250mL beaker and ultrasonically oscillated for 2H, and 10.25mL of H is dropwise added2PtCl6(0.1mol/L) solution and 16.97mL of CoCl2(0.1mol/L) solution, then adding 21mL formic acid, stirring at room temperature for 30min, placing in a microwave oven, heating for 20s, stopping heating for 10s, repeating for 5 times, then heating for 10s, stopping heating for 10s, repeating for 5 times, cooling, filtering, and drying in vacuum to obtain the Pt-Co/C catalyst.
Example 5: preparation examples
Taking 0.6g Vulcan XC-72 carbon powder and 0.1g144CeO2Adding the powder into 0.7mol HCOOH aqueous solution, ultrasonic treating for 30min, heating the obtained suspension to 80 deg.C, and stirring to obtain 10.25mL H2PtCl6(0.1mol/L) solution and 9.4mL of PdCl2(0.1mol/L) solution was added dropwise to the suspension. Stirring was continued at 80 ℃ for 2h to ensure complete reduction of Pd and Pt. After cooling, the mixture is washed with ultrapure water by suction filtration for a plurality of times until no Cl is formed-Until now. Finally, the obtained catalyst is put in a drying oven at 60 ℃ for vacuum drying to obtain Pt-Pd-144CeO2a/C catalyst.
Example 6: comparative preparation example
Adding 0.6g Vulcan XC-72 carbon powder into 0.7mol HCOOH aqueous solution, ultrasonically treating for 30min, heating the obtained suspension to 80 deg.C, and stirring to obtain 10.25mL H2PtCl6(0.1mol/L) solution and 9.4mL of PdCl2(0.1mol/L) solution was added dropwise to the suspension. Stirring was continued at 80 ℃ for 2h to ensure complete reduction of Pd and Pt. After cooling, the mixture is washed with ultrapure water by suction filtration for a plurality of times until no Cl is formed-Until now. And finally, putting the obtained catalyst in a 60 ℃ oven for vacuum drying to obtain the Pt-Pd/C catalyst.
Example 7: preparation examples
Taking 0.6g Vulcan XC-72 active carbon, 0.1g144CeO2Powder, 10.25mL of H2PtCl6(0.1mol/L) solution, 5.08mLHAuCl4(0.1mol/L) solution and 17.04mL of NiSO4(0.1mol/L) of the solution was mixed and added to 80mL of ultrapure water, and the resulting suspension was sonicated for 1 hour. 200mL of Ethylene Glycol (EG) solution was added, and after 1 hour of sonication, the resulting solution was heated to 90 ℃ in a water bath with constant stirring for 4 hours. Cooling to room temperature, filtering, washing the obtained catalyst with a mixed solution of distilled water and ethanol for several times, and drying in vacuum at 60 ℃ to obtain Pt-Au-Ni-144CeO2a/C catalyst.
Example 8: comparative preparation example
0.6g of Vulcan XC-72 activated carbon and 10.25mL of H are taken2PtCl6(0.1mol/L) solution, 5.08mL of HAuCl4(0.1mol/L) solution and 17.04mL of NiSO4(0.1mol/L) of the solution was mixed and added to 80mL of ultrapure water, and the resulting suspension was sonicated for 1 hour. 200mL of Ethylene Glycol (EG) solution was added, and after 1 hour of sonication, the resulting solution was heated to 90 ℃ in a water bath with constant stirring for 4 hours. After cooling to room temperature and filtering, the obtained catalyst is washed by a mixed solution of distilled water and ethanol for several times and dried in vacuum at 60 ℃ to obtain the Pt-Au-Ni/C catalyst.
Example 9: preparation examples
0.6g of brown yellow graphene oxide and 0.1g of brown yellow graphene oxide are taken144CeO2Adding the powder into 50mL deionized water, ultrasonically dispersing for 30min, and transferring 10.25mL H by using a liquid transfer gun2PtCl6(0.1mol/L) solution, 17.04mL of NiSO4(0.1mol/L) solution and 15.74mL of CuCl2(0.1mol/L) solution is mixed and added into the graphene oxide solution, stirred for 10min and then transferred into a double-neck flask, 9.5mL deionized water is added, and N is added at 0 DEG C2After being mixed evenly in the atmosphere, 5mL7.72mmol/L KBH is injected rapidly by an injector4The solution changes color from brown yellow to black, and continues to be at 0 ℃ and N2Stirring for 30min under gas atmosphere to make it fully react, finally filtering, washing, drying and grinding to obtain Pt-Ni-Cu-144CeO2a/C catalyst.
Example 10: comparative preparation example
Adding 0.6g of brown yellow graphene oxide into 50mL of deionized water, performing ultrasonic dispersion for 30min, and using a liquid-transferring gunRemove 10.25mL of H2PtCl6(0.1mol/L) solution, 17.04mL of NiSO4(0.1mol/L) solution and 15.74mL of CuCl2(0.1mol/L) solution is mixed and added into the graphene oxide solution, stirred for 10min and then transferred into a double-neck flask, 9.5mL deionized water is added, and N is added at 0 DEG C2After being mixed evenly in the atmosphere, 5mL of KBH 7.72mmol/L is injected rapidly by a syringe4The solution changes color from brown yellow to black, and continues to be at 0 ℃ and N2Stirring for 30min under gas atmosphere to make the catalyst fully react, finally carrying out suction filtration, washing, drying and grinding to obtain the Pt-Ni-Cu/C catalyst.
Example 11: preparation examples
Taking 0.6g Vulcan XC-72 active carbon, 0.1g144CeO2Adding the powder into a mixed solution of ultrapure water and isopropanol (volume ratio of 2:1), and ultrasonically dispersing for 0.5 h. Then, 10.25mL of H is added dropwise in sequence2PtCl6(0.1mol/L) solution, 9.4mL of PdCl2(0.1mol/L) solution and 15.74mL of CuCl2(0.1mol/L) solution and 20mg sodium citrate, and stirred for 1 h. Adjusting the pH of the solution>And 12, heating to 80 ℃, slowly dropwise adding 0.2mol/L excessive sodium borohydride solution, and keeping for 2 hours. Then continuously stirring for 3h at room temperature, filtering and washing, and blowing and drying at 60 ℃ to obtain Pt-Pd-Cu-144CeO2a/C catalyst.
Example 12: comparative preparation example
0.6g of Vulcan XC-72 activated carbon is taken and added into a mixed solution of ultrapure water and isopropanol (volume ratio is 2:1) for ultrasonic dispersion for 0.5 h. Then, 10.25mL of H is added dropwise in sequence2PtCl6(0.1mol/L) solution, 9.4mL of PdCl2(0.1mol/L) solution and 15.74mL of CuCl2(0.1mol/L) solution and 20mg sodium citrate, and stirred for 1 h. Adjusting the pH of the solution>And 12, heating to 80 ℃, slowly dropwise adding 0.2mol/L excessive sodium borohydride solution, and keeping for 2 hours. And then, continuously stirring for 3 hours at room temperature, carrying out suction filtration and washing, and carrying out forced air drying at 60 ℃ to obtain the Pt-Pd-Cu/C catalyst.
Example 13: preparation examples
Separating natural by using isotope separation method and using CAE-1 type magnetic separation equipment of nuclear institute of atomic energy science of ChinaIsotopically abundant Sm2O3The concrete operating conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameter Sm-151-100. Collecting the separated Sm at a discharge port2O3Sm-151 in 100% abundance by ICP-MS detection, thus obtaining151Sm2O3(prepared analogously to the following examples)151Sm2O3)。
0.6g of Vulcan XC-72 carbon powder and 0.1g of carbon powder are taken151Sm2O3Powder, 10.25mL of H2PtCl6(0.1mol/L) solution and 17.04mL of NiSO4(0.1mol/L) solution is mixed and added into 80mL deionized water, ultrasonic treatment is carried out for 30min to lead the solution to be dispersed evenly, then under stirring, 1mol/L NaOH solution is used for adjusting the pH value to 8-9, and excessive NaBH of 2.0mg/mL is slowly added4The solution was stirred for 3 h. Washing with ultrapure water until no Cl is formed-Then vacuum drying at 60 ℃ for 4h to obtain Pt-Ni-151Sm2O3a/C catalyst.
Example 14: preparation examples
0.6g of Vulcan XC-72 carbon powder and 0.1g of carbon powder are taken151Sm2O3The powder is added into a 250mL beaker together with 80mL of ethylene glycol, ultrasonically shaken for 2H, and 10.25mL of H is added dropwise2PtCl6(0.1mol/L) solution and 16.97mL of CoCl2(0.1mol/L) solution, then adding 21mL formic acid, stirring at room temperature for 30min, placing in a microwave oven to heat for 20s and 10s for 5 times, then heating for 10s and 10s for 5 times, cooling, filtering, vacuum drying to obtain Pt-Co-151Sm2O3a/C catalyst.
Example 15: preparation examples
Taking 0.6g Vulcan XC-72 carbon powder and 0.1g151Sm2O3Adding the powder into 0.7mol HCOOH aqueous solution, ultrasonic treating for 30min, heating the obtained suspension to 80 deg.C, and stirring to obtain 10.25mL H2PtCl6(0.1mol/L) solution and 9.4mL of PdCl2(0.1mol/L) solution was added dropwise to the suspension. Stirring was continued at 80 ℃ for 2h to ensure complete reduction of Pd and Pt. After cooling, the mixture is washed by ultrapure water in a suction filtration manner for a plurality of times until noCl-Until now. Finally, the obtained catalyst is put in a drying oven at 60 ℃ for vacuum drying to obtain Pt-Pd-151Sm2O3a/C catalyst.
Example 16: preparation examples
Taking 0.6g Vulcan XC-72 active carbon, 0.1g151Sm2O3Powder, 10.25mL of H2PtCl6(0.1mol/L) solution, 5.08mL of HAuCl4(0.1mol/L) solution and 17.04mL of NiSO4(0.1mol/L) of the solution was mixed and added to 80mL of ultrapure water, and the resulting suspension was sonicated for 1 hour. 200mL of Ethylene Glycol (EG) solution was added, and after 1 hour of sonication, the resulting solution was heated to 90 ℃ in a water bath with constant stirring for 4 hours. Cooling to room temperature, filtering, washing the obtained catalyst with a mixed solution of distilled water and ethanol for several times, and drying in vacuum at 60 ℃ to obtain Pt-Au-Ni-151Sm2O3a/C catalyst.
Example 17: preparation examples
0.6g of brown yellow graphene oxide and 0.1g of brown yellow graphene oxide are taken151Sm2O3Adding the powder into 50mL deionized water, ultrasonically dispersing for 30min, and transferring 10.25mL H by using a liquid transfer gun2PtCl6(0.1mol/L) solution, 17.04mL of NiSO4(0.1mol/L) solution and 15.74mL of CuCl2(0.1mol/L) solution is mixed and added into the graphene oxide solution, stirred for 10min and then transferred into a double-neck flask, 9.5mL deionized water is added, and N is added at 0 DEG C2After being mixed evenly in the atmosphere, 5mL7.72mmol/L KBH is injected rapidly by an injector4The solution changes color from brown yellow to black, and continues to be at 0 ℃ and N2Stirring for 30min under gas atmosphere to make it fully react, finally filtering, washing, drying and grinding to obtain Pt-Ni-Cu-151Sm2O3a/C catalyst.
Example 18: preparation examples
Taking 0.6g Vulcan XC-72 active carbon, 0.1g151Sm2O3Adding the powder into a mixed solution of ultrapure water and isopropanol (volume ratio of 2:1), and ultrasonically dispersing for 0.5 h. Then, 10.25mL of H is added dropwise in sequence2PtCl6(0.1mol/L) solution, 9.4mL of PdCl2(0.1mol/L) solution and 15.74mL of CuCl2(0.1mol/L) solution and 20mg sodium citrate, and stirred for 1 h. Adjusting the pH of the solution>And 12, heating to 80 ℃, slowly dropwise adding 0.2mol/L excessive sodium borohydride solution, and keeping for 2 hours. Then continuously stirring for 3h at room temperature, filtering and washing, and blowing and drying at 60 ℃ to obtain Pt-Pd-Cu-151Sm2O3a/C catalyst.
Example 19: preparation examples
Separating natural isotopic abundance Gd by using a CAE-1 type magnetic separation device of nuclear institute of atomic energy science of China, based on the principle of isotope separation method2O3The concrete operating conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameter Gd-153-100. Collecting the separated Gd at a discharge port2O3Gd-153 abundance as 100% by ICP-MS detection, thereby obtaining153Gd2O3(prepared analogously to the following examples)153Gd2O3)。
0.6g of Vulcan XC-72 carbon powder and 0.1g of carbon powder are taken153Gd2O3Powder, 10.25mL of H2PtCl6(0.1mol/L) solution and 17.04mL of NiSO4(0.1mol/L) solution is mixed and added into 80mL deionized water, ultrasonic treatment is carried out for 30min to lead the solution to be dispersed evenly, then under stirring, 1mol/L NaOH solution is used for adjusting the pH value to 8-9, and excessive NaBH of 2.0mg/mL is slowly added4The solution was stirred for 3 h. Washing with ultrapure water until no Cl is formed-Then vacuum drying at 60 ℃ for 4h to obtain Pt-Ni-153Gd2O3a/C catalyst.
Example 20: preparation examples
0.6g of Vulcan XC-72 carbon powder and 0.1g of carbon powder are taken153Gd2O3The powder is added into a 250mL beaker together with 80mL of ethylene glycol, ultrasonically shaken for 2H, and 10.25mL of H is added dropwise2PtCl6(0.1mol/L) solution and 16.97mL of CoCl2(0.1mol/L) solution, then adding 21mL formic acid, stirring at room temperature for 30min, placing in a microwave oven to heat for 20s and 10s for 5 times, then heating for 10s and 10s for 5 times, cooling, filtering, vacuum drying to obtain Pt-Co-153Gd2O3a/C catalyst.
Example 21: preparation examples
Taking 0.6g Vulcan XC-72 carbon powder and 0.1g153Gd2O3Adding the powder into 0.7mol HCOOH aqueous solution, ultrasonic treating for 30min, heating the obtained suspension to 80 deg.C, and stirring to obtain 10.25mL H2PtCl6(0.1mol/L) solution and 9.4mL of PdCl2(0.1mol/L) solution was added dropwise to the suspension. Stirring was continued at 80 ℃ for 2h to ensure complete reduction of Pd and Pt. After cooling, the mixture is washed with ultrapure water by suction filtration for a plurality of times until no Cl is formed-Until now. Finally, the obtained catalyst is put in a drying oven at 60 ℃ for vacuum drying to obtain Pt-Pd-153Gd2O3a/C catalyst.
Example 22: preparation examples
Taking 0.6g Vulcan XC-72 active carbon, 0.1g153Gd2O3Powder, 10.25mL of H2PtCl6(0.1mol/L) solution, 5.08mL of HAuCl4(0.1mol/L) solution and 17.04mL of NiSO4(0.1mol/L) of the solution was mixed and added to 80mL of ultrapure water, and the resulting suspension was sonicated for 1 hour. 200mL of Ethylene Glycol (EG) solution was added, and after 1 hour of sonication, the resulting solution was heated to 90 ℃ in a water bath with constant stirring for 4 hours. Cooling to room temperature, filtering, washing the obtained catalyst with a mixed solution of distilled water and ethanol for several times, and drying in vacuum at 60 ℃ to obtain Pt-Au-Ni-153Gd2O3a/C catalyst.
Example 23: preparation examples
0.6g of brown yellow graphene oxide and 0.1g of brown yellow graphene oxide are taken153Gd2O3Adding the powder into 50mL deionized water, ultrasonically dispersing for 30min, and transferring 10.25mL H by using a liquid transfer gun2PtCl6(0.1mol/L) solution, 17.04mL of NiSO4(0.1mol/L) solution and 15.74mL of CuCl2(0.1mol/L) solution is mixed and added into the graphene oxide solution, stirred for 10min and then transferred into a double-neck flask, 9.5mL deionized water is added, and N is added at 0 DEG C2After being mixed evenly in the atmosphere, 5mL7.72mmol/L KBH is injected rapidly by an injector4Solution, the color of the solution is changed from brown to yellowTurning black, continuing at 0 ℃ N2Stirring for 30min under gas atmosphere to make it fully react, finally filtering, washing, drying and grinding to obtain Pt-Ni-Cu-153Gd2O3a/C catalyst.
Example 24: preparation examples
Taking 0.6g Vulcan XC-72 active carbon, 0.1g153Gd2O3Adding the powder into a mixed solution of ultrapure water and isopropanol (volume ratio of 2:1), and ultrasonically dispersing for 0.5 h. Then, 10.25mL of H is added dropwise in sequence2PtCl6(0.1mol/L) solution, 9.4mL of PdCl2(0.1mol/L) solution and 15.74mL of CuCl2(0.1mol/L) solution and 20mg sodium citrate, and stirred for 1 h. Adjusting the pH of the solution>And 12, heating to 80 ℃, slowly dropwise adding 0.2mol/L excessive sodium borohydride solution, and keeping for 2 hours. Then continuously stirring for 3h at room temperature, filtering and washing, and blowing and drying at 60 ℃ to obtain Pt-Pd-Cu-153Gd2O3a/C catalyst.
Example 25: preparation examples
Separating Tb from natural isotope abundance by CAE-1 type magnetic separation device of nuclear institute of atomic energy science of China based on isotope separation method2O3The concrete operating conditions are as follows: the vaporization temperature is 2500 ℃, the magnetic field voltage is 1000V, and the magnetic separation parameters Tb-157-. Collecting separated Tb at discharge port2O3Tb-157 abundance was 100% by ICP-MS, thus obtaining157Tb2O3(prepared analogously to the following examples)157Tb2O3)。
0.6g of Vulcan XC-72 carbon powder and 0.1g of carbon powder are taken157Tb2O3Powder, 10.25mL of H2PtCl6(0.1mol/L) solution and 17.04mL of NiSO4(0.1mol/L) solution is mixed and added into 80mL deionized water, ultrasonic treatment is carried out for 30min to lead the solution to be dispersed evenly, then under stirring, 1mol/L NaOH solution is used for adjusting the pH value to 8-9, and excessive NaBH of 2.0mg/mL is slowly added4The solution was stirred for 3 h. Washing with ultrapure water until no Cl is formed-Then vacuum drying at 60 ℃ for 4h to obtain Pt-Ni-157Tb2O3a/C catalyst.
Example 26: preparation examples
0.6g of Vulcan XC-72 carbon powder and 0.1g of carbon powder are taken157Tb2O3The powder is added into a 250mL beaker together with 80mL of ethylene glycol, ultrasonically shaken for 2H, and 10.25mL of H is added dropwise2PtCl6(0.1mol/L) solution and 16.97mL of CoCl2(0.1mol/L) solution, then adding 21mL formic acid, stirring at room temperature for 30min, placing in a microwave oven to heat for 20s and 10s for 5 times, then heating for 10s and 10s for 5 times, cooling, filtering, vacuum drying to obtain Pt-Co-157Tb2O3a/C catalyst.
Example 27: preparation examples
Taking 0.6g Vulcan XC-72 carbon powder and 0.1g157Tb2O3Adding the powder into 0.7mol HCOOH aqueous solution, ultrasonic treating for 30min, heating the obtained suspension to 80 deg.C, and stirring to obtain 10.25mL H2PtCl6(0.1mol/L) solution and 9.4mL of PdCl2(0.1mol/L) solution was added dropwise to the suspension. Stirring was continued at 80 ℃ for 2h to ensure complete reduction of Pd and Pt. After cooling, the mixture is washed with ultrapure water by suction filtration for a plurality of times until no Cl is formed-Until now. Finally, the obtained catalyst is put in a drying oven at 60 ℃ for vacuum drying to obtain Pt-Pd-157Tb2O3a/C catalyst.
Example 28: preparation examples
Taking 0.6g Vulcan XC-72 active carbon, 0.1g157Tb2O3Powder, 10.25mL of H2PtCl6(0.1mol/L) solution, 5.08mL of HAuCl4(0.1mol/L) solution and 17.04mL of NiSO4(0.1mol/L) of the solution was mixed and added to 80mL of ultrapure water, and the resulting suspension was sonicated for 1 hour. 200mL of Ethylene Glycol (EG) solution was added, and after 1 hour of sonication, the resulting solution was heated to 90 ℃ in a water bath with constant stirring for 4 hours. Cooling to room temperature, filtering, washing the obtained catalyst with a mixed solution of distilled water and ethanol for several times, and drying in vacuum at 60 ℃ to obtain Pt-Au-Ni-157Tb2O3a/C catalyst.
Example 29: preparation examples
0.6g of brown yellow graphene oxide and 0.1g of brown yellow graphene oxide are taken157Tb2O3Adding the powder into 50mL deionized water, ultrasonically dispersing for 30min, and transferring 10.25mL H by using a liquid transfer gun2PtCl6(0.1mol/L) solution, 17.04mL of NiSO4(0.1mol/L) solution and 15.74mL of CuCl2(0.1mol/L) solution is mixed and added into the graphene oxide solution, stirred for 10min and then transferred into a double-neck flask, 9.5mL deionized water is added, and N is added at 0 DEG C2After being mixed evenly in the atmosphere, 5mL7.72mmol/L KBH is injected rapidly by an injector4The solution changes color from brown yellow to black, and continues to be at 0 ℃ and N2Stirring for 30min under gas atmosphere to make it fully react, finally filtering, washing, drying and grinding to obtain Pt-Ni-Cu-157Tb2O3a/C catalyst.
Example 30: preparation examples
Taking 0.6g Vulcan XC-72 active carbon, 0.1g157Tb2O3Adding the powder into a mixed solution of ultrapure water and isopropanol (volume ratio of 2:1), and ultrasonically dispersing for 0.5 h. Then, 10.25mL of H is added dropwise in sequence2PtCl6(0.1mol/L) solution, 9.4mL of PdCl2(0.1mol/L) solution and 15.74mL of CuCl2(0.1mol/L) solution and 20mg sodium citrate, and stirred for 1 h. Adjusting the pH of the solution>And 12, heating to 80 ℃, slowly dropwise adding 0.2mol/L excessive sodium borohydride solution, and keeping for 2 hours. Then continuously stirring for 3h at room temperature, filtering and washing, and blowing and drying at 60 ℃ to obtain Pt-Pd-Cu-157Tb2O3a/C catalyst.
Example 31: stability test examples
The stability of the catalysts obtained in examples 1 to 30 was determined separately by the following specific method: and testing the I-t curve of the catalyst by using an electrochemical workstation three-electrode system, and judging the stability of the catalyst according to the I-t curve, wherein a glassy carbon electrode coated with the catalyst in a dripping mode is used as a working electrode, a saturated calomel electrode is used as a reference electrode, and a platinum wire electrode is used as a counter electrode. The solution to be tested is 0.5mol/L C2H5OH+0.5mol/L H2SO4High purity nitrogen was passed through the solution for 15 minutes prior to testing to eliminate oxygen interference. Test potential of all catalystsThe uniform value is 0.6V, and the test time is 1000 s. The results are shown in table 1 below.
Table 1 catalyst stability test results
Figure BDA0002501964640000121
Figure BDA0002501964640000131
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations. The foregoing examples or embodiments are merely illustrative of the present invention, which may be embodied in other specific forms or in other specific forms without departing from the spirit or essential characteristics thereof. The described embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. The scope of the invention should be indicated by the appended claims, and any changes that are equivalent to the intent and scope of the claims should be construed to be included therein.

Claims (7)

1. A platinum-based catalyst containing a lanthanide element or compound, characterized in that: the platinum-based catalyst comprises a catalytic active substance and a catalytic auxiliary substance, wherein the catalytic active substance comprises metal platinum, the catalytic auxiliary substance comprises a cocatalyst, and the cocatalyst comprises one or more of elementary substances or compounds of lanthanide monoisotope cerium-144, samarium-151, gadolinium-153 or terbium-157.
2. The platinum-based catalyst according to claim 1, characterized in that: the mass ratio of the catalytic active substance to the catalytic auxiliary substance is 1: 0.01-10.
3. The platinum-based catalyst according to claim 1, characterized in that: the mass ratio of the catalytic active substance to the cocatalyst is 1: 0.0001-1.
4. The platinum-based catalyst according to claim 1, characterized in that: the catalyst promoter also comprises one or more of simple substances or oxides of gold, silver, cobalt, nickel, palladium, ruthenium, tin, bismuth, copper, iron, iridium, manganese, molybdenum, rhodium, tungsten and zinc.
5. The platinum-based catalyst according to claim 1, characterized in that: the catalytic auxiliary substance also comprises a catalyst carrier which is selected from one or more of active carbon, silicon carbide, aluminum oxide, graphene, silicon dioxide and zeolite.
6. The platinum-based catalyst according to claim 1, characterized in that: the compound is an inorganic compound or an organic compound.
7. The platinum-based catalyst according to claim 1, characterized in that: the compound is an oxide.
CN202010435137.5A 2020-05-21 2020-05-21 Platinum-based catalyst containing lanthanide element simple substance or compound Pending CN111659386A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010435137.5A CN111659386A (en) 2020-05-21 2020-05-21 Platinum-based catalyst containing lanthanide element simple substance or compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010435137.5A CN111659386A (en) 2020-05-21 2020-05-21 Platinum-based catalyst containing lanthanide element simple substance or compound

Publications (1)

Publication Number Publication Date
CN111659386A true CN111659386A (en) 2020-09-15

Family

ID=72384174

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010435137.5A Pending CN111659386A (en) 2020-05-21 2020-05-21 Platinum-based catalyst containing lanthanide element simple substance or compound

Country Status (1)

Country Link
CN (1) CN111659386A (en)

Similar Documents

Publication Publication Date Title
CN105431230B (en) Method for forming noble metal nanoparticles on a support
CN113422073B (en) Preparation method of cobalt-modified carbon-supported superfine platinum nano alloy catalyst
CN115036522B (en) Method for preparing alloy catalyst for fuel cell by limited field
CN108745373A (en) A kind of preparation method of precious metal alloys/carbon material supported type catalyst
CN111659388A (en) Platinum-based catalyst containing uranium or uranium compound
CN107537517B (en) Alloy colloid and preparation method and application thereof
CN111509242A (en) Electrode catalyst for fuel cell and method for activating catalyst
CN106784900B (en) Carbon nano tube covered by platinum-based nano particle coated tin dioxide and preparation method thereof
CN102600835A (en) Preparation method of hollow carbon nanocage loaded platinum-based composite catalysts
CN111916771B (en) High-activity and high-stability PtNi nano-alloy catalyst and preparation method and application thereof
CN107088415B (en) Preparation method of platinum alloy nano powder catalyst
CN112553646A (en) MXene loaded nano alloy catalyst, preparation method and application thereof
CN113707897A (en) Anti-reversal catalyst for fuel cell and preparation method thereof
CN109499602B (en) Synthesis method for systematically regulating and controlling number of atoms of load type iron atom cluster
JP2004332028A (en) Ternary metallic colloid having three layer core/shell structure and method for producing ternary metallic colloid
CN112186199B (en) Catalyst for solid polymer fuel cell and preparation method thereof
CN111659383A (en) Platinum-based catalyst containing cesium or compound thereof
CN111659387A (en) Platinum-based catalyst containing thorium or compound thereof
CN111659389A (en) Platinum-based catalyst containing actinide simple substance or compound
CN111659384A (en) Platinum-based catalyst containing plutonium or plutonium compound
CN110575830A (en) platinum-containing catalyst and preparation method and application thereof
CN111659390A (en) Platinum-based catalyst containing promethium or compound thereof
CN115557469B (en) Amorphous noble metal oxide material and preparation method and application thereof
CN111659386A (en) Platinum-based catalyst containing lanthanide element simple substance or compound
CN111659416A (en) Platinum-based catalyst containing strontium or strontium compound

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20200915

RJ01 Rejection of invention patent application after publication