CN110190288B - Preparation method of carbon-supported rhodium-lead symbiotic catalyst for ethanol electrooxidation - Google Patents

Preparation method of carbon-supported rhodium-lead symbiotic catalyst for ethanol electrooxidation Download PDF

Info

Publication number
CN110190288B
CN110190288B CN201910136553.2A CN201910136553A CN110190288B CN 110190288 B CN110190288 B CN 110190288B CN 201910136553 A CN201910136553 A CN 201910136553A CN 110190288 B CN110190288 B CN 110190288B
Authority
CN
China
Prior art keywords
carbon
catalyst
lead
rhodium
ethanol
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.)
Expired - Fee Related
Application number
CN201910136553.2A
Other languages
Chinese (zh)
Other versions
CN110190288A (en
Inventor
阳耀月
兰冰
杨鸿均
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.)
Southwest Minzu University
Original Assignee
Southwest Minzu University
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 Southwest Minzu University filed Critical Southwest Minzu University
Priority to CN201910136553.2A priority Critical patent/CN110190288B/en
Publication of CN110190288A publication Critical patent/CN110190288A/en
Application granted granted Critical
Publication of CN110190288B publication Critical patent/CN110190288B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • H01M4/925—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

Abstract

The invention discloses a carbon-supported rhodium-lead alloy-lead oxide (RhpB-PbO) for ethanol electro-oxidation under alkaline condition x A preparation method of/C) symbiotic catalyst, belonging to the technical field of fuel cell anode catalyst and novel material. A rhodium-lead alloy nanoparticle-lead oxide nanoparticle symbiotic structure is constructed on the surface of carbon by adopting a simple ethylene glycol one-pot reduction method, and the method is simple and easy to operate and is convenient for industrial mass production. The catalyst obtained by the method obviously improves the catalytic activity and stability of the ethanol electrooxidation under the alkaline condition and the selectivity of a carbon dioxide product. Wherein the catalytic activity of the ethanol oxidation is as high as 2700mA/mgRhAnd is 3.8 times of that of the commercial carbon-supported palladium catalyst at the same potential. The catalytic activity remained 58% after 3 hours stability testing, and the faradaic efficiency of ethanol oxidation to carbon dioxide product increased to 20% which is 5 times that of commercial palladium on carbon catalyst. The catalyst will probably promote the commercial application of direct alkaline ethanol fuel cells.

Description

Preparation method of carbon-supported rhodium-lead symbiotic catalyst for ethanol electrooxidation
Technical Field
The invention relates to the technical field of fuel cell anode catalysts and novel materials, in particular to a preparation method of a direct alkaline ethanol fuel cell anode catalyst.
Background
The energy problem is a major strategic problem related to the safety of the people in the country and even the state. The research and development of new energy with high efficiency, safety and environmental protection are main approaches for solving the problems of current energy and environment and are also important pushers for promoting the adjustment and transformation of energy structures in China. As a novel and efficient energy conversion device, a fuel cell is one of strategic key points in the development of new energy in various countries.
Among various fuel cells, the direct alkaline ethanol fuel cell attracts attention because of the advantages of ethanol safety, innocuity, wide source, high energy density (8.01 kWh/Kg), and the like. It takes ethanol as fuel molecule, generates acetic acid and (/ or) carbon dioxide through the oxidation of anode catalyst and releases electrons. At present, the widely reported ethanol electro-oxidation catalysts are platinum and palladium based catalysts, and the biggest problem of the catalysts is that the products of the catalytic oxidation of ethanol are mainly acetic acid, and only 4 units of electrons are transferred in the process; but will convert 12 units of electrons if the ethanol is oxidized to carbon dioxide. The efficiency of completely oxidizing ethanol to generate carbon dioxide by using platinum and palladium based catalysts is low (the data reported at present is 5-10%), and a novel ethanol electro-oxidation catalyst with higher efficiency is urgently needed to be developed.
Interestingly, recent studies have shown that rhodium (Rh) catalysts can effectively cleave ethanol C-C bonds, increasing the selectivity of catalyzing ethanol to carbon dioxide. The carbon-supported rhodium catalyst reported by Zhongnan university Zhongde Bie subject group and the rhodium quintuplex twin crystal nano single crystal reported by Xiamen university Siemens subject group all show better C-C bond breaking activity than platinum and palladium-based catalysts. However, the rhodium component, although having a relatively strong C-C bond cleavage ability, gives reaction intermediates (CO and CH) x ) But is difficult to remove by oxidation on the rhodium surface, and thus a significant catalyst poisoning phenomenon occurs. According to the Langmuir-Hinshelwood reaction mechanism, the situation that the introduction of the oxophilic component near rhodium can greatly improve is possible, and the introduction is also an important catalyst design idea of the invention.
Based on the situation, the development of an ethanol electro-oxidation catalyst which takes rhodium as a basic component and combines with the construction of an oxophilic component to obtain high efficiency and high selectivity is a scheme for solving the problems and has practical significance for promoting the development of ethanol fuel cells.
Disclosure of Invention
The invention provides a carbon-supported rhodium-lead alloy-lead oxide symbiotic high-efficiency catalyst (RhpB-PbO) for ethanol electrooxidation under alkaline condition x The preparation method of the compound is shown in the specification. Specifically, the invention adopts a simple ethylene glycol one-pot reduction method to construct a rhodium-lead alloy nanoparticle-lead oxide nanoparticle symbiotic structure on the carbon surface, mainly utilizes the breaking capacity of a rhodium component to a C-C bond of ethanol and the oxophilicity of lead oxide to provide a large number of oxygen-containing species, and synergistically and greatly improves the activity and stability of ethanol electrooxidation and the selectivity of a carbon dioxide product. The method is simple and easy to operate, and is convenient for industrial production.
The technical scheme adopted by the invention is that the high-efficiency RhpB-PbO is realized in one step by utilizing the reduction action of glycol on metal precursor salt at high temperature (160 ℃) and the adsorption loading action of activated carbon on nano particles x Preparation of the/C catalyst. The method specifically comprises the following steps:
firstly, dispersing trivalent rhodium salt, divalent lead salt and a carbon source into ethylene glycol according to a certain proportion, and fully stirring to obtain uniform slurry;
next, the pH of the slurry was adjusted to 9.5 with sodium hydroxide glycol solution, followed by reduction at 160 ℃ under high purity nitrogen blanket and vigorous stirring.
And finally, after the slurry is cooled to room temperature, regulating the pH value of the slurry to 3.5 by hydrochloric acid to achieve the purpose of gel breaking, and continuously stirring to ensure that the metal colloidal particles are fully adsorbed and loaded on the carbon surface. And filtering the slurry, washing a filter cake by using a large amount of ultrapure water, and drying to obtain the catalyst.
In the invention, the carbon source can be Vulcan XC-72 activated carbon, carbon nano tubes, graphene oxide and other carbon sources.
In the invention, the trivalent rhodium salt is all water-soluble rhodium salts, including rhodium chloride, rhodium nitrate and the like.
In the invention, the divalent lead salt is all water-soluble divalent lead salts, including lead acetate, lead nitrate and the like.
In the present invention, the ratio of the trivalent rhodium salt, the divalent lead salt and the carbon source may be any mass ratio. The best case catalyst (example 1) had a molar ratio of rhodium to lead of 3:2 and a mass ratio of metal to carbon of 4: 1.
The invention has the beneficial effects that the catalytic activity and stability of the obtained catalyst on the ethanol electrooxidation and the selectivity of the carbon dioxide product are greatly improved. The best case catalyst (example 1) has catalytic activity of ethanol oxidation as high as 3639mA/mgRh, which is 3.8 times that of the commercial palladium-on-carbon catalyst at the same potential (0.6V vs. RHE) (FIG. 3). After 3 hours of stability test, the catalytic activity of the catalyst still remains 58 percent, and under the same condition, the catalytic activity of the carbon-supported Pd catalyst is basically reduced to zero. More importantly, the faradaic efficiency of the catalyst for complete oxidation of ethanol to carbon dioxide is increased to 20%, well above 5% of commercial palladium on carbon catalysts. In addition, the catalyst is simple to prepare, strong in operability and easy for large-scale industrial production.
Drawings
FIG. 1 is an X-ray diffraction characterization chart of the best case catalyst (example 1).
FIG. 2 is a transmission electron micrograph of the best case catalyst (example 1).
FIG. 3 is a graph showing the electrooxidation activity of ethanol under alkaline conditions
FIG. 4 is a graph showing stability tests of the best case catalyst (example 1).
Figure 5 is a graph comparing faradaic efficiency of ethanol electrooxidation under alkaline conditions.
Detailed Description
The following will further explain the implementation of the preparation method by combining the drawings and the specific embodiment.
Example 1: adding 7.48 mL of 1M sodium citrate aqueous solution into 100mL of ethylene glycol solution, mixing well, adding 18 mL of 0.05M Pb (CH)3COOH)2Solution and 12 mL of 0.05M RhCl3The solution was ultrasonically dispersed for 30 minutes, 60 mg of activated carbon was added thereto, and vigorously stirred for 8 hours to obtain a slurry. Adjusting the pH of the solution to 9.5 with freshly prepared 1M sodium hydroxide in ethylene glycol to obtain a solution containing high purity N2Stirring vigorously under atmosphere, heating slowly to 160 deg.C, holding for 3 hr, cooling to room temperature, adjusting pH to 3.5 with 1M hydrochloric acid, and stirring under high purity nitrogen atmosphere for 2 hr. Then filtering, washing a filter cake by using a large amount of ultrapure water, and grinding the dried filter cake to obtain the catalyst. The molar ratio of rhodium to lead of the catalyst obtained in this embodiment was 6:4, and the mass ratio of metal to carbon was 4: 1. The catalyst obtained by the embodiment is the case catalyst with the best activity and stability.
FIG. 1 is an X-ray diffraction characterization of the best case catalyst (example 1) showing the formation of a rhodium-lead alloy phase and a small amount of lead oxide for the resulting catalyst. FIG. 2 is a transmission electron microscopy characterization of the best case catalyst (example 1) showing the intergrowth of the rhodium-lead alloy and lead oxide with the rhodium-lead metal nanoparticles having an average particle size of about 5 nm and the intergrowth of the lead oxide nanoparticles having an average particle size of about 4 nm. FIG. 3 is a test chart of the electrooxidation activity and stability of ethanol under alkaline conditions, and activity tests show that the catalyst in case 1 has the catalytic activity of ethanol oxidation mass as high as 2700mA/mgRh, and is 3.8 times higher than that of a commercial palladium-on-carbon catalyst under the same potential. FIG. 4 is a graph of stability tests for the best case catalyst (example 1) showing that the case catalyst retained 58% of its catalytic activity and the commercial palladium on carbon catalyst dropped to zero after the 3 hour stability test. Figure 5 is a graph of faradaic efficiency for the electro-oxidation of ethanol to carbon dioxide under alkaline conditions, with faradaic efficiency for the case catalyst fully oxidized to carbon dioxide increased to 20%, much higher than 5% for the palladium on carbon catalyst.
Example 2: in the embodiment, the effectiveness of the synthesis scheme is verified by changing the addition ratio of the metal salt. Adding 7.48 mL of 1M sodium citrate aqueous solution into 100mL of ethylene glycol solution, mixing well, and adding 5.87 mL of 0.05 MPb (CH)3COOH)2Solution and 5.87 mL of 0.05M RhCl3The solution was ultrasonically dispersed for 30 minutes, 60 mg of activated carbon was added thereto, and vigorously stirred for 8 hours to obtain a slurry. Adjusting the pH of the solution to 9.5 with freshly prepared 1M sodium hydroxide in ethylene glycol to obtain a solution containing high purity N2Stirring vigorously under atmosphere, heating slowly to 160 deg.C, holding for 3 hr, cooling to room temperature, adjusting pH to 3.5 with 1M hydrochloric acid, and purifying with high purity N2Stirring was continued under atmosphere for 2 hours. Then filtering, washing a filter cake by using a large amount of ultrapure water, and grinding the dried filter cake to obtain the catalyst. The molar ratio of rhodium to lead of the catalyst obtained in this embodiment was 4:4, and the mass ratio of metal to carbon was 3: 2. The catalytic activity of the catalyst obtained in this scheme is two thirds of that of case 1 (see FIG. 3), indicating that the rhodium-lead ratio has a significant effect on the activity of the catalyst.
Example 3: in the embodiment, the effectiveness of the synthesis scheme is verified by changing the addition ratio of the metal salt. Adding 7.48 mL of 1M sodium citrate aqueous solution into 100mL of ethylene glycol solution, mixing well, and adding 1.95 mL of 0.05 MPb (CH)3COOH)2Solution and 3.90 mL of 0.05M RhCl3The solution was ultrasonically dispersed for 30 minutes, 60 mg of activated carbon was added thereto, and vigorously stirred for 8 hours to obtain a slurry. Adjusting the pH of the solution to 9.5 with freshly prepared 1M NaOH glycol solution under high purity N2Stirring vigorously under atmosphere, heating slowly to 160 deg.C, holding for 3 hr, cooling to room temperature, adjusting pH of the solution to 3.5 with 1M HCl, and adding N2Stirring was continued under atmosphere for 2 hours.Then filtering, washing a filter cake by using a large amount of ultrapure water, and grinding the dried filter cake to obtain the catalyst. The molar ratio of rhodium to lead of the catalyst obtained in this embodiment was 4:4, and the mass ratio of metal to carbon was 3: 2. The catalytic activity of the catalyst obtained in this scheme is one-half of that of case 1 (see FIG. 3), which illustrates that the ratio of rhodium to lead has a significant effect on the activity of the catalyst.

Claims (9)

1. A preparation method of carbon-supported rhodium-lead alloy-lead oxide symbiotic catalyst for ethanol electrooxidation under alkaline conditions is characterized in that a rhodium-lead alloy nanoparticle-lead oxide nanoparticle symbiotic structure is constructed on the carbon surface by adopting a simple ethylene glycol one-pot reduction method, the rhodium-lead alloy nanoparticles are used as key active points for ethanol C-C bond fracture, the lead oxide nanoparticles are used as oxygen-containing species providers, and the activity and stability of ethanol electrooxidation and the selectivity of carbon dioxide products under alkaline conditions are synergistically improved; the method comprises the following specific steps: firstly, dispersing trivalent rhodium salt, divalent lead salt and a carbon source into ethylene glycol according to a certain proportion, and fully stirring to obtain uniform slurry; secondly, adjusting the pH value of the slurry to 9.5 by using a freshly prepared sodium hydroxide glycol solution, and then heating to 160 ℃ under the protection of high-purity nitrogen and vigorous stirring to reduce metal salt; finally, after the slurry is cooled to room temperature, the pH value of the slurry is adjusted by hydrochloric acid to achieve the purpose of gel breaking, and the slurry is continuously stirred under the protection of nitrogen to strengthen the adsorption load of the nano particles on carbon; then filtering and washing a filter cake by using a large amount of ultrapure water, and drying to obtain the catalyst.
2. The method of claim 1, further comprising: the carbon source is Vulcan XC-72 activated carbon or carbon nano-tubes or graphene oxide.
3. The method of claim 1, further comprising: trivalent rhodium salts are all water-soluble rhodium salts.
4. The method of claim 3, further comprising: the water-soluble rhodium salt is rhodium chloride or rhodium nitrate.
5. The method of claim 1, further comprising: the divalent lead salt is all water-soluble divalent lead salts.
6. The method of claim 5, further comprising: the water-soluble divalent lead salt is lead acetate or lead nitrate.
7. The method of claim 1, further comprising: the proportions of the trivalent rhodium salt, the divalent lead salt and the carbon source are in any mass ratio.
8. The method of claim 1, further comprising: the molar ratio of rhodium to lead was 3:2 and the mass ratio of metal to carbon was 4: 1.
9. The method of claim 1, further comprising: under the alkaline condition, the catalytic activity of the obtained catalyst on the oxidation of ethanol is higher than 2700mA/mgRh, the catalytic activity is higher than 58% of the initial value after 3-hour stability test, and the Faraday efficiency of the complete oxidation of ethanol into carbon dioxide is higher than 20%.
CN201910136553.2A 2019-02-25 2019-02-25 Preparation method of carbon-supported rhodium-lead symbiotic catalyst for ethanol electrooxidation Expired - Fee Related CN110190288B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910136553.2A CN110190288B (en) 2019-02-25 2019-02-25 Preparation method of carbon-supported rhodium-lead symbiotic catalyst for ethanol electrooxidation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910136553.2A CN110190288B (en) 2019-02-25 2019-02-25 Preparation method of carbon-supported rhodium-lead symbiotic catalyst for ethanol electrooxidation

Publications (2)

Publication Number Publication Date
CN110190288A CN110190288A (en) 2019-08-30
CN110190288B true CN110190288B (en) 2020-06-12

Family

ID=67713632

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910136553.2A Expired - Fee Related CN110190288B (en) 2019-02-25 2019-02-25 Preparation method of carbon-supported rhodium-lead symbiotic catalyst for ethanol electrooxidation

Country Status (1)

Country Link
CN (1) CN110190288B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115337925A (en) * 2022-07-15 2022-11-15 西南民族大学 Electrochemical method for modifying lead atom skin layer on surface of carbon-supported rhodium nanoparticle

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102969514A (en) * 2012-12-03 2013-03-13 哈尔滨工业大学 Metal-coated oxide nano core-shell structure catalyst and preparation method thereof
CN104485463A (en) * 2014-12-30 2015-04-01 西北师范大学 Alloy-oxide composite carbon material noble-metal-loaded catalyst and preparation method of catalyst
CN104707603A (en) * 2013-12-15 2015-06-17 中国科学院大连化学物理研究所 Pt-PbOx/C catalyst and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102969514A (en) * 2012-12-03 2013-03-13 哈尔滨工业大学 Metal-coated oxide nano core-shell structure catalyst and preparation method thereof
CN104707603A (en) * 2013-12-15 2015-06-17 中国科学院大连化学物理研究所 Pt-PbOx/C catalyst and preparation method thereof
CN104485463A (en) * 2014-12-30 2015-04-01 西北师范大学 Alloy-oxide composite carbon material noble-metal-loaded catalyst and preparation method of catalyst

Also Published As

Publication number Publication date
CN110190288A (en) 2019-08-30

Similar Documents

Publication Publication Date Title
Yan et al. CeO2 particles anchored to Ni2P nanoplate for efficient photocatalytic hydrogen evolution
CN107349937B (en) Preparation method of graphene-based bimetallic sulfide nano composite photocatalyst
Liang et al. MOFs-derived core-shell Co3Fe7@ Fe2N nanopaticles supported on rGO as high-performance bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions
Wang et al. Recent developments in the use of single-atom catalysts for water splitting
CN112103520B (en) Anode catalyst of alcohol fuel cell
WO2013143326A1 (en) Wc/cnt, wc/cnt/pt composite material and preparation process therefor and use thereof
Wang et al. Synergistic effect between strongly coupled CoAl layered double hydroxides and graphene for the electrocatalytic reduction of oxygen
CN112169790B (en) Method for preparing high-load noble metal monoatomic catalyst by in-situ photo-reduction method
CN108550871B (en) Manganese dioxide/carbon black composite material and preparation method and application thereof
CN111905766B (en) 0D/1D W18O49Preparation method and application of/CdS Z-type visible light catalyst
CN109718823B (en) N-doped TiO2/C composite material and preparation method and application thereof
Shao et al. Oxygen vacancy-rich N-doped carbon encapsulated BiOCl-CNTs heterostructures as robust electrocatalyst synergistically promote oxygen reduction and Zn-air batteries
CN112705193B (en) Porous carbon self-reduction preparation method of porous carbon loaded small-size noble metal nanoparticle composite material
CN110190288B (en) Preparation method of carbon-supported rhodium-lead symbiotic catalyst for ethanol electrooxidation
CN112962109B (en) Preparation method and application of antimony-doped copper/cuprous oxide electro-catalytic material
CN102389836A (en) Polyaniline/titanium dioxide/clay nanometer composite photocatalyst and preparation method thereof
CN110961101B (en) Platinum-based catalyst, preparation method and application thereof
CN111686766B (en) Metal-fluorine doped carbon composite material, preparation method thereof and application thereof in electrocatalytic nitrogen fixation
WO2024011905A1 (en) Metal-supported spinel nickel manganite nanosphere aerogel, preparation method therefor and use thereof
CN108607546B (en) Electrocatalyst with platinum loaded on titanium dioxide-carbon composite carrier and preparation method thereof
CN108091890B (en) Preparation method of silver-cobalt-guanine-based nano flaky material
CN114843535A (en) Boron-doped palladium-based catalyst for fuel cell and preparation method thereof
CN114824319A (en) N-doped TiO 2-x Preparation method and application of supported PtCu alloy nano catalyst
CN113241451A (en) Low-platinum alloy catalyst prepared by crystal face, preparation method thereof and application thereof in fuel cell
CN114308061A (en) NiAu bimetallic alloy nano catalyst and synthesis and application thereof

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
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20200612

CF01 Termination of patent right due to non-payment of annual fee