CN112563517B - Preparation method of rare earth metal doped carbon-based oxygen reduction electrocatalyst - Google Patents

Preparation method of rare earth metal doped carbon-based oxygen reduction electrocatalyst Download PDF

Info

Publication number
CN112563517B
CN112563517B CN202011417932.8A CN202011417932A CN112563517B CN 112563517 B CN112563517 B CN 112563517B CN 202011417932 A CN202011417932 A CN 202011417932A CN 112563517 B CN112563517 B CN 112563517B
Authority
CN
China
Prior art keywords
rare earth
earth metal
oxygen reduction
doped carbon
based oxygen
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.)
Active
Application number
CN202011417932.8A
Other languages
Chinese (zh)
Other versions
CN112563517A (en
Inventor
赵江红
覃宇鹏
周玮
赵永祥
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.)
Shanxi University
Original Assignee
Shanxi 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 Shanxi University filed Critical Shanxi University
Priority to CN202011417932.8A priority Critical patent/CN112563517B/en
Publication of CN112563517A publication Critical patent/CN112563517A/en
Application granted granted Critical
Publication of CN112563517B publication Critical patent/CN112563517B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)

Abstract

A preparation method of a rare earth metal doped carbon-based oxygen reduction electrocatalyst belongs to the technical field of new energy materials and electrocatalysis, and can solve the problem of the existing oxygen reduction electrocatalystThe activity and stability of the catalyst are determined by reacting aromatic compound containing carboxyl/aldehyde group/amino/hydroxyl functional group as carbon source, nitrogen-containing organic compound as nitrogen source, rare earth metal salt and Fe/Co/Ni transition metal salt as metal precursor in proper solvent to form stable metal complex, polymerizing the material in N solvent by means of solvent-thermal method, and final polymerizing2And roasting and carbonizing at high temperature under the protection of atmosphere, and then carrying out acid washing, washing and centrifuging to obtain the rare earth metal doped carbon-based oxygen reduction electrocatalyst. The rich 4f electrons of the rare earth elements can effectively regulate and control the electronic structure of the catalyst, and the rare earth elements and the Fe/Co/Ni main metal have synergistic effect, so that the activity and the stability of the carbon-based oxygen reduction electrocatalyst are improved.

Description

Preparation method of rare earth metal doped carbon-based oxygen reduction electrocatalyst
Technical Field
The invention belongs to the technical field of new energy materials and electrocatalysis, and particularly relates to a preparation method of a rare earth metal doped carbon-based oxygen reduction electrocatalyst.
Background
With the rapid development of society, the demand of people for clean energy is more and more urgent due to the non-regenerability and pollution of the traditional fossil energy. A clean and efficient energy conversion device such as a fuel cell or a metal-air battery has higher conversion efficiency than a conventional device for converting energy by combustion, and is therefore favored by the academic world and the industry and is one of key technologies for the future widespread use of clean energy. However, the poor activity and stability of the cathode oxygen reduction electrocatalyst have been the core factors that prevent the popularization and application of such technologies, and commercial application still depends on the Pt/C catalyst at present. The scale of energy utilization is huge, and the Pt/C catalyst still cannot support the large-scale development of technologies such as fuel cells and the like due to the defects of low natural reserves, high price, poor stability, easiness in CO and methanol poisoning and the like of precious metal Pt. Therefore, suitable efficient and inexpensive alternative catalysts are still being sought.
Non-noble metal catalysts (NPMCs) are ideal materials for replacing Pt/C catalysts, and common NPMCs comprise pure carbon materials doped with nonmetal S, P, O, N, B and the like, carbon-based transition metal materials, and non-noble metal catalysts such as transition metal sulfides, phosphides, oxides, nitrides and the like. The carbon-based transition metal catalyst forms active sites capable of regulating and controlling an internal electronic structure of the catalyst with a carbon structure by means of electron-rich or electron-deficient elements such as metal-N-C, S, P, O, N, B and the like, so that the activation energy of the oxygen electrocatalytic reduction reaction can be remarkably reduced, and the catalytic performance and the stability of the oxygen electrocatalytic reduction reaction are enhanced. The 4f orbit filled with the rare earth element can improve the electronic environment, so that the rare earth metal is introduced into the carbon-based catalytic material, the oxygen electrocatalytic reduction activity of the carbon-based catalytic material is hopeful to be improved, and meanwhile, the valence-variable characteristic of the rare earth element can enable the rare earth element to become a reaction site of a peroxide intermediate, so that the stability of the catalyst is improved.
Disclosure of Invention
The invention provides a method for preparing a rare earth metal doped carbon-based oxygen reduction electrocatalyst with high catalytic activity and good stability, aiming at the problems of activity and stability of the existing oxygen reduction electrocatalyst.
The invention adopts the following technical scheme:
a preparation method of a rare earth metal doped carbon-based oxygen reduction electrocatalyst comprises the following steps:
firstly, putting a nitrogen source, a carbon source, a rare earth metal salt and a Fe/Co/Ni transition metal salt into a container, adding a solvent, sealing and heating to 40-80 ℃, stirring for 4-12h, adding formaldehyde, and continuously stirring for 10-16h to obtain a metal-organic complex precursor;
secondly, transferring the metal-organic complex precursor obtained in the first step into a reaction container, and carrying out solvothermal reaction for 20-24h at the temperature of 100-200 ℃;
thirdly, placing the product obtained in the second step in a muffle furnace, and heating and oxidizing in air at the temperature of 150-;
fourthly, placing the product obtained in the third step into a tubular furnace, and carbonizing at the temperature of 800-1000 ℃ for 1-3h under the nitrogen atmosphere;
and fifthly, washing the carbonized product obtained in the fourth step by 0.5M sulfuric acid and deionized water to be neutral, and centrifugally drying to obtain the rare earth metal doped carbon-based oxygen reduction electrocatalyst.
In the first step, the nitrogen source is a nitrogen-containing organic substance, and comprises at least one of melamine, urea, phenanthroline, dicyandiamide and bipyridine.
In the first step, the carbon source is an aromatic compound containing carboxyl/aldehyde/amino/hydroxyl functional groups, and comprises at least one of 2, 4-dihydroxybenzoic acid, 2, 4-dihydroxybenzaldehyde, aminophenol, aminobenzoic acid, hydroxyquinoline, aminoquinoline, hydroxynaphthalene, aminonaphthalene, hydroxynaphthoic acid, aminonaphthoic acid, hydroxypyridine, carboxypyridine, hydroxypyrrole and carboxypyrrole.
In the first step the rare earth metal salt comprises at least one of hydrated chlorides of lanthanum, cerium, neodymium, samarium, gadolinium, erbium and yttrium.
The Fe/Co/Ni transition metal salt in the first step comprises at least one of hydrated chlorides of Fe/Co/Ni.
The solvent in the first step comprises at least one of water, ethanol and ethylene glycol.
In the first step, the molar ratio of the Fe/Co/Ni transition metal salt to the rare earth metal salt to the carbon source to the nitrogen source to formaldehyde is 1: (0.1-0.5): (1-2): (2-5): (1-1).
In the third step, the oxidation heating rate of the muffle furnace is 1-5 ℃/min.
The carbonization heating rate in the fourth step is 1-3 ℃/min.
The invention has the following beneficial effects:
the rare earth elements have rich 4f electrons, and the excellent oxygen affinity and variable valence thereof can often promote the activity of a main catalytic active site in an oxidation-reduction reaction and are beneficial to the adsorption and migration of oxygen species. Meanwhile, the doping of the rare earth elements can form oxygen vacancies, which is beneficial to stabilizing the catalyst, can effectively regulate and control the electronic structure and the electron transfer performance of the catalyst, and can obviously improve the activity and the stability of the carbon-based oxygen reduction electrocatalyst under the synergistic action with the Fe/Co/Ni main metal.
Drawings
FIG. 1 inventive example 12 ORR Linear sweep polarization curves of cerium doped carbon based Co electrocatalyst (Co (Ce) -61) in 0.1M KOH.
Fig. 2 is an ORR linear scan polarization curve for Ce-only single metal doped catalyst in 0.1M KOH.
FIG. 3 is an ORR linear scan polarization curve for Co-only single metal doped catalysts in 0.1M KOH.
FIG. 4 is an ORR linear scan polarization curve before and after stability test of cerium doped carbon based Co electrocatalyst (Co (Ce) -61) in 0.1M KOH.
Fig. 5 is a Tafel slope plot for a series of cerium doped carbon-based Co electrocatalysts.
FIG. 6 is the calculated electron transfer number from the K-L equation for a series of cerium doped carbon based Co electrocatalysts.
Figure 7 is an XRD diffractogram of a series of cerium doped carbon based Co electrocatalysts.
Detailed Description
Example 1
11.51mmol of 2, 4-dihydroxybenzoic acid, 7.77mmol of melamine, 12.80mmol of cobalt chloride hexahydrate (CoCl)2·6H2O) and 3.20mmol of lanthanum chloride heptahydrate (LaCl)3·7H2O) is placed in a container, 18mL of deionized water and 4mL of absolute ethyl alcohol are added, the mixture is stirred for 10 hours at 50 ℃, 48.9mmol of formaldehyde is added, and the mixture is continuously stirred and reacts for 14 hours; then transferring the mixture into a hydrothermal kettle to react for 24 hours at the temperature of 120 ℃; then moving the mixture into a muffle furnace to be oxidized for 4 hours at 280 ℃ in a stage-by-stage manner at the heating rate of 1 ℃/min; transferring the oxidized product into a tubular furnace, heating to 900 ℃ in a staged manner at the heating rate of 1 ℃/min under the nitrogen atmosphere, carbonizing, and preserving heat for 2 hours; cooling to room temperature, washing with 0.5M dilute sulfuric acid, washing with deionized water to neutrality, centrifuging, and drying to obtain the metal-doped carbon-based oxygen reduction electrocatalyst. The serial number of the catalyst is Co (La) -41, and the loading capacity of the prepared catalyst on a glassy carbon electrode is 0.2018 mg-cm-2The limiting current density at the rotation speed of 2025rpm was 5.85 mA cm-2The initial potential was 0.817V vs. RHE.
Example 2
11.51mmol of 2, 4-dihydroxybenzoic acid, 7.77mmol of melamine, 12.80mmol of cobalt chloride hexahydrate (CoCl)2·6H2O) and 3.20mmol gadolinium chloride hexahydrate (GdCl)3·6H2O) into a container, 18mL of deionized water and 4mL of absolute ethanol are added, 50 DEG CStirring for 10h, adding 48.9mmol of formaldehyde, and continuously stirring for reacting for 14 h; then transferring the mixture into a hydrothermal kettle to react for 24 hours at the temperature of 120 ℃; then moving the mixture into a muffle furnace to be oxidized for 4 hours at 280 ℃ in a stage-by-stage manner at the heating rate of 1 ℃/min; transferring the oxidation product into a tubular furnace, gradually heating to 900 ℃ at the heating rate of 1 ℃/min under the nitrogen atmosphere, carbonizing, and preserving heat for 2 hours; cooling to room temperature, washing with 0.5M dilute sulfuric acid, washing with deionized water to neutrality, centrifuging, and drying to obtain the rare earth metal doped carbon-based oxygen reduction electrocatalyst. The serial number of the catalyst is Co (Gd) -41, and the loading capacity of the prepared catalyst on a glassy carbon electrode is 0.2018 mg-cm-2The limiting current density at the rotation speed of 2025rpm was 4.51 mA/cm-2The initial potential was 0.825V vs. RHE.
Example 3
11.51mmol of 2, 4-dihydroxybenzoic acid, 7.77mmol of melamine, 12.80mmol of cobalt chloride hexahydrate (CoCl)2·6H2O) and 3.20mmol of erbium chloride hexahydrate (ErCl)3·6H2O) is placed in a container, 18mL of deionized water and 4mL of absolute ethyl alcohol are added, the mixture is stirred for 10 hours at 50 ℃, 48.9mmol of formaldehyde is added, and the mixture is continuously stirred and reacts for 14 hours; then transferring the mixture into a hydrothermal kettle to react for 24 hours at the temperature of 120 ℃; then moving the mixture into a muffle furnace to be oxidized for 4 hours at 280 ℃ in a stage-by-stage manner at the heating rate of 1 ℃/min; transferring the oxidation product into a tubular furnace, gradually heating to 900 ℃ at the heating rate of 1 ℃/min under the nitrogen atmosphere, carbonizing, and preserving heat for 2 hours; cooling to room temperature, washing with 0.5M dilute sulfuric acid, washing with deionized water to neutrality, centrifuging, and drying to obtain the rare earth metal doped carbon-based oxygen reduction electrocatalyst. The serial number of the catalyst is Co (Er) -41, and the loading capacity of the prepared catalyst on a glassy carbon electrode is 0.2018 mg-cm-2The limiting current density at the rotation speed of 2025rpm was 4.96mA cm-2The initial potential was 0.799V vs. RHE.
Example 4
11.51mmol of 2, 4-dihydroxybenzoic acid, 7.77mmol of melamine, 12.80mmol of cobalt chloride hexahydrate (CoCl)2·6H2O) and 3.20mmol of neodymium chloride hexahydrate (NdCl)3·6H2O) is put into a container, 18mL of deionized water and 4mL of absolute ethyl alcohol are added, the mixture is stirred for 10 hours at 50 ℃, 48.9mmol of formaldehyde is added, and the mixture is stirred continuouslyThe reaction time is 14 hours; then transferring the mixture into a hydrothermal kettle to react for 24 hours at the temperature of 120 ℃; then moving the mixture into a muffle furnace to be oxidized for 4 hours at 280 ℃ in a stage-by-stage manner at the heating rate of 1 ℃/min; transferring the oxidation product into a tubular furnace, gradually heating to 900 ℃ at the heating rate of 1 ℃/min under the nitrogen atmosphere, carbonizing, and preserving heat for 2 hours; cooling to room temperature, washing with 0.5M dilute sulfuric acid, washing with deionized water to neutrality, centrifuging, and drying to obtain the rare earth metal doped carbon-based oxygen reduction electrocatalyst. The serial number of the catalyst is Co (Nd) -41, and the loading capacity of the prepared catalyst on a glassy carbon electrode is 0.2018 mg-cm-2The limiting current density at the rotation speed of 2025rpm was 5.18 mA cm-2The initial potential was 0.868V vs. RHE.
Example 5
11.51mmol of 2, 4-dihydroxybenzoic acid, 7.77mmol of melamine, 12.80mmol of cobalt chloride hexahydrate (CoCl)2·6H2O) and 6.40mmol of samarium chloride hexahydrate (SmCl)3·6H2O) is placed in a container, 18mL of deionized water and 4mL of absolute ethyl alcohol are added, the mixture is stirred for 10 hours at 50 ℃, 48.9mmol of formaldehyde is added, and the mixture is continuously stirred and reacts for 14 hours; then transferring the mixture into a hydrothermal kettle to react for 24 hours at the temperature of 120 ℃; then moving the mixture into a muffle furnace to be oxidized for 4 hours at 280 ℃ in a stage-by-stage manner at the heating rate of 1 ℃/min; transferring the oxidation product into a tubular furnace, gradually heating to 900 ℃ at the heating rate of 1 ℃/min under the nitrogen atmosphere, carbonizing, and preserving heat for 2 hours; cooling to room temperature, washing with 0.5M dilute sulfuric acid, washing with deionized water to neutrality, centrifuging, and drying to obtain the rare earth metal doped carbon-based oxygen reduction electrocatalyst. The serial number of the catalyst is Co (Sm) -21, and the loading capacity of the prepared catalyst on a glassy carbon electrode is 0.2018 mg-cm-2The limiting current density at the rotation speed of 2025rpm was 6.97 mA/cm-2Initial potential of 0.887V vs. RHE, electron transfer number of 3.74, Tafel slope of 47 mV dec-1。
Example 6
11.51mmol of 2, 4-dihydroxybenzoic acid, 7.77mmol of melamine, 12.80mmol of cobalt chloride hexahydrate (CoCl)2·6H2O) and 3.20mmol of samarium chloride hexahydrate (SmCl)3·6H2O) is put into a container, 18mL of deionized water and 4mL of absolute ethyl alcohol are added, the mixture is stirred for 10h at 50 ℃, and 48.9mmol of methanol is addedContinuously stirring the aldehyde for reaction for 14 hours; then transferring the mixture into a hydrothermal kettle to react for 24 hours at the temperature of 120 ℃; then moving the mixture into a muffle furnace to be oxidized for 4 hours at 280 ℃ in a stage-by-stage manner at the heating rate of 1 ℃/min; transferring the oxidation product into a tubular furnace, gradually heating to 900 ℃ at the heating rate of 1 ℃/min under the nitrogen atmosphere, carbonizing, and preserving heat for 2 hours; cooling to room temperature, washing with 0.5M dilute sulfuric acid, washing with deionized water to neutrality, centrifuging, and drying to obtain the rare earth metal doped carbon-based oxygen reduction electrocatalyst. . The serial number of the catalyst is Co (Sm) -41, and the loading capacity of the prepared catalyst on a glassy carbon electrode is 0.2018 mg-cm-2The limiting current density at the rotation speed of 2025rpm was 6.13 mA cm-2Initial potential of 0.880V vs. RHE, electron transfer number of 3.62, Tafel slope of 55 mV dec-1。
Example 7
11.51mmol of 2, 4-dihydroxybenzoic acid, 7.77mmol of melamine, 12.80mmol of cobalt chloride hexahydrate (CoCl)2·6H2O) and 6.40mmol of yttrium chloride hexahydrate (YCl)3·6H2O) is placed in a container, 18mL of deionized water and 4mL of absolute ethyl alcohol are added, stirring is carried out for 10h at 50 ℃, 48.9mmol of formaldehyde is added, and stirring reaction is continued for 14 h; then transferring the mixture into a hydrothermal kettle to react for 24 hours at the temperature of 120 ℃; then moving the mixture into a muffle furnace to be oxidized for 4 hours at 280 ℃ in a stage-by-stage manner at the heating rate of 1 ℃/min; transferring the oxidized product into a tubular furnace, heating to 900 ℃ in a staged manner at the heating rate of 1 ℃/min under the nitrogen atmosphere, carbonizing, and preserving heat for 2 hours; cooling to room temperature, washing with 0.5M dilute sulfuric acid, washing with deionized water to neutrality, centrifuging, and drying to obtain the rare earth/alkaline earth-cobalt-nitrogen co-doped catalyst. The serial number of the catalyst is Co (Y) -21, and the loading capacity of the prepared catalyst on a glassy carbon electrode is 0.2018 mg-cm-2The limiting current density at the rotation speed of 2025rpm was 7.08 mA/cm-2Initial potential of 0.875V vs. RHE, electron transfer number of 3.86, Tafel slope of 50 mV dec-1。
Example 8
11.51mmol of 2, 4-dihydroxybenzoic acid, 7.77mmol of melamine, 12.80mmol of cobalt chloride hexahydrate (CoCl)2·6H2O) and 3.20mmol of Yttrium chloride hexahydrate (YCl)3·6H2O) is placed in a container and addedStirring 18mL of deionized water and 4mL of absolute ethyl alcohol at 50 ℃ for 10h, adding 48.9mmol of formaldehyde, and continuously stirring for reacting for 14 h; then transferring the mixture into a hydrothermal kettle to react for 24 hours at the temperature of 120 ℃; then moving the mixture into a muffle furnace to be oxidized for 4 hours at 280 ℃ in a stage-by-stage manner at the heating rate of 1 ℃/min; transferring the oxidation product into a tubular furnace, gradually heating to 900 ℃ at the heating rate of 1 ℃/min under the nitrogen atmosphere, carbonizing, and preserving heat for 2 hours; cooling to room temperature, washing with 0.5M dilute sulfuric acid, washing with deionized water to neutrality, centrifuging, and drying to obtain the rare earth/alkaline earth-cobalt-nitrogen co-doped catalyst. The serial number of the catalyst is Co (Y) -41, and the loading capacity of the prepared catalyst on a glassy carbon electrode is 0.2018 mg-cm-2The limiting current density at the rotation speed of 2025rpm was 6.80 mA/cm-2Initial potential of 0.885V vs. RHE, electron transfer number of 3.78, Tafel slope of 53 mV dec-1。
Example 9
11.51mmol of 2, 4-dihydroxybenzoic acid, 7.77mmol of melamine, 12.80mmol of cobalt chloride hexahydrate (CoCl)2·6H2O) and 3.20mmol of yttrium chloride hexahydrate (YCl)3·6H2O) is placed in a container, 18mL of deionized water and 4mL of absolute ethyl alcohol are added, the mixture is stirred for 10 hours at 70 ℃, 48.9mmol of formaldehyde is added, and the mixture is continuously stirred and reacts for 14 hours; then transferring the mixture into a hydrothermal kettle to react for 24 hours at the temperature of 120 ℃; then moving the mixture into a muffle furnace to be oxidized for 4 hours at 280 ℃ in a stage-by-stage manner at the heating rate of 1 ℃/min; transferring the oxidation product into a tubular furnace, gradually heating to 900 ℃ at the heating rate of 1 ℃/min under the nitrogen atmosphere, carbonizing, and preserving heat for 2 hours; cooling to room temperature, washing with 0.5M dilute sulfuric acid, washing with deionized water to neutrality, centrifuging, and drying to obtain the rare earth metal doped carbon-based oxygen reduction electrocatalyst. The serial number of the catalyst is Co (Y) -41-70, and the loading capacity of the prepared catalyst on a glassy carbon electrode is 0.2018mg cm-2The limiting current density at the rotation speed of 2025rpm was 6.69 mA cm-2Initial potential of 0.881V vs. RHE, electron transfer number of 3.63, Tafel slope of 47 mV dec-1。
Example 10
11.51mmol of 2, 4-dihydroxybenzoic acid, 7.77mmol of melamine, 12.80mmol of cobalt chloride hexahydrate (CoCl)2·6H2O) and 3.20mmol hexahydrateYttrium chloride (YCl)3·6H2O) is placed in a container, 18mL of deionized water and 4mL of absolute ethyl alcohol are added, stirring is carried out for 10h at 70 ℃, 48.9mmol of formaldehyde is added, and stirring reaction is continued for 14 h; then transferring the mixture into a hydrothermal kettle to react for 24 hours at the temperature of 180 ℃; then moving the mixture into a muffle furnace to be oxidized for 4 hours at 280 ℃ in a stage-by-stage manner at the heating rate of 1 ℃/min; transferring the oxidation product into a tubular furnace, gradually heating to 900 ℃ at the heating rate of 1 ℃/min under the nitrogen atmosphere, carbonizing, and preserving heat for 2 hours; cooling to room temperature, washing with 0.5M dilute sulfuric acid, washing with deionized water to neutrality, centrifuging, and drying to obtain the rare earth metal doped carbon-based oxygen reduction electrocatalyst. The serial number of the catalyst is Co (Y) -180-41, and the loading capacity of the prepared catalyst on a glassy carbon electrode is 0.2018mg cm-2The limiting current density at the rotation speed of 2025rpm was 6.99 mA cm-2Initial potential of 0.889V vs. RHE, electron transfer number of 3.87, Tafel slope of 49 mV dec-1。
Example 11
11.51mmol of 2, 4-dihydroxybenzoic acid, 7.77mmol of melamine, 12.80mmol of cobalt chloride hexahydrate (CoCl)2·6H2O) and 6.40mmol of cerium chloride heptahydrate (CeCl)3·7H2O) is placed in a container, 18mL of deionized water and 4mL of absolute ethyl alcohol are added, the mixture is stirred for 10 hours at 50 ℃, 48.9mmol of formaldehyde is added, and the mixture is continuously stirred and reacts for 14 hours; then transferring the mixture into a hydrothermal kettle to react for 24 hours at the temperature of 120 ℃; then moving the mixture into a muffle furnace to be oxidized for 4 hours at 280 ℃ in a stage-by-stage manner at the heating rate of 1 ℃/min; transferring the oxidation product into a tubular furnace, gradually heating to 900 ℃ at the heating rate of 1 ℃/min under the nitrogen atmosphere, carbonizing, and preserving heat for 2 hours; cooling to room temperature, washing with 0.5M dilute sulfuric acid, washing with deionized water to neutrality, centrifuging, and drying to obtain the rare earth metal doped carbon-based oxygen reduction electrocatalyst. The serial number of the catalyst is Co (Ce) -21, and the loading capacity of the prepared catalyst on a glassy carbon electrode is 0.2018 mg-cm-2The limiting current density at the rotation speed of 2025rpm was 6.62mA cm-2Initial potential of 0.888V vs. RHE, electron transfer number of 4.06, Tafel slope of 66 mV dec-1。
Example 12
11.51mmol of 2, 4-dihydroxybenzoic acid, 7.77mmol of melamine and 12.80mmol of cobalt chloride hexahydrate (CoCl)2·6H2O) and 3.20mmol of cerium chloride heptahydrate (CeCl)3·7H2O) is placed in a container, 18mL of deionized water and 4mL of absolute ethyl alcohol are added, the mixture is stirred for 10 hours at 50 ℃, 48.9mmol of formaldehyde is added, and the mixture is continuously stirred and reacts for 14 hours; then transferring the mixture into a hydrothermal kettle to react for 24 hours at the temperature of 120 ℃; then moving the mixture into a muffle furnace to be oxidized for 4 hours at 280 ℃ in a stage-by-stage manner at the heating rate of 1 ℃/min; transferring the oxidation product into a tubular furnace, gradually heating to 900 ℃ at the heating rate of 1 ℃/min under the nitrogen atmosphere, carbonizing, and preserving heat for 2 hours; cooling to room temperature, washing with 0.5M dilute sulfuric acid, washing with deionized water to neutrality, centrifuging, and drying to obtain the rare earth metal doped carbon-based oxygen reduction electrocatalyst. The serial number of the catalyst is Co (Ce) -41, and the loading capacity of the prepared catalyst on a glassy carbon electrode is 0.2018 mg-cm-2The limiting current density at the rotation speed of 2025rpm was 6.46mA cm-2Initial potential of 0.812V vs. RHE, electron transfer number of 4.03, Tafel slope of 82 mV dec-1。
Example 13
11.51mmol of 2, 4-dihydroxybenzoic acid, 7.77mmol of melamine, 12.80mmol of cobalt chloride hexahydrate (CoCl)2·6H2O) and 2.13mmol of cerium chloride heptahydrate (CeCl)3·7H2O) is placed in a container, 18mL of deionized water and 4mL of absolute ethyl alcohol are added, stirring is carried out for 10h at 50 ℃, 48.9mmol of formaldehyde is added, and stirring reaction is continued for 14 h; then transferring the mixture into a hydrothermal kettle to react for 24 hours at the temperature of 120 ℃; then moving the mixture into a muffle furnace to be oxidized for 4 hours at 280 ℃ in a stage-by-stage manner at the heating rate of 1 ℃/min; transferring the oxidation product into a tubular furnace, gradually heating to 900 ℃ at the heating rate of 1 ℃/min under the nitrogen atmosphere, carbonizing, and preserving heat for 2 hours; cooling to room temperature, washing with 0.5M dilute sulfuric acid, washing with deionized water to neutrality, centrifuging, and drying to obtain the rare earth metal doped carbon-based oxygen reduction electrocatalyst. The serial number of the catalyst is Co (Ce) -61, and the loading capacity of the prepared catalyst on a glassy carbon electrode is 0.2018 mg-cm-2The limiting current density at the rotation speed of 2025rpm was 7.15mA cm-2Initial potential of 0.923V vs. RHE, electron transfer number of 4.36, Tafel slope of 67 mV dec-1。
Example 14
11.51mmol of 2, 4-dihydroxybenzoic acid, 7.77mmol of melamine, 12.80mmol of cobalt chloride hexahydrate (CoCl)2·6H2O) and 1.60mmol of cerium chloride heptahydrate (CeCl)3·7H2O) is placed in a container, 18mL of deionized water and 4mL of absolute ethyl alcohol are added and stirred for 10h, 48.9mmol of formaldehyde is added and stirring reaction is continued for 14 h; then transferring the mixture into a hydrothermal kettle to react for 24 hours at the temperature of 120 ℃; then moving the mixture into a muffle furnace to be oxidized for 4 hours at 280 ℃ in a stage-by-stage manner at the heating rate of 1 ℃/min; transferring the oxidation product into a tubular furnace, gradually heating to 900 ℃ at the heating rate of 1 ℃/min under the nitrogen atmosphere, carbonizing, and preserving heat for 2 hours; cooling to room temperature, washing with 0.5M dilute sulfuric acid, washing with deionized water to neutrality, centrifuging, and drying to obtain the rare earth metal doped carbon-based oxygen reduction electrocatalyst. The serial number of the catalyst is Co (Ce) -81, and the loading capacity of the prepared catalyst on a glassy carbon electrode is 0.2018 mg-cm-2The limiting current density at the rotation speed of 2025rpm was 6.59 mA/cm-2Initial potential of 0.875V vs. RHE, electron transfer number of 3.86, Tafel slope of 73 mV dec-1。
Taking the cerium-doped carbon-based Co electrocatalyst (Co (Ce) -61) prepared by the invention as an example, the rare earth metal-doped carbon-based oxygen reduction electrocatalyst prepared by the invention and the electrochemical performance thereof are illustrated.
FIG. 1 is an ORR linear scan polarization curve of a cerium doped carbon based Co electrocatalyst (Co (Ce) -61) in 0.1M KOH with an onset potential of 0.923V vs. RHE and a limiting current density of 5.07 mA-cm-2. Compared with the single metal doped catalyst, the initial potential and the limiting current density are greatly improved, the reaction activity and the conductivity are obviously improved, and the synergistic effect of the rare earth metal and the transition metal cobalt in the catalytic process is proved.
FIGS. 2 and 3 are ORR linear scanning polarization curves of a single-metal Ce-doped catalyst and a single-metal Co-doped catalyst in 0.1M KOH, respectively, the initial potentials of the catalysts are 0.775V vs. RHE and 0.880V vs. RHE, respectively, and the limiting current densities of the catalysts are 3.43 mA-cm-2And 4.45mA · cm-2。
FIG. 4 is an ORR linear scan polarization curve before and after stability test of cerium doped carbon based Co electrocatalyst (Co (Ce) -61) in 0.1M KOH. As can be seen from FIG. 4, after 1500 CV cycles (20 h) of the test, the half-wave potential was shifted only by 23mV negatively, and the limiting current density remained 94.8% of the initial value, showing good stability.
FIG. 5 is a Tafel slope plot for a cerium doped carbon based Co electrocatalyst with a Tafel slope at 70 mV dec-1About, the Tafel slope of the Co (Ce) -61 catalyst is 67 mV dec-1The good dynamic process is demonstrated.
Fig. 6 shows the electron transfer number calculated by the K-L equation for the series of cerium-doped carbon-based Co electrocatalysts, and as can be seen from fig. 6, the electron transfer number catalyzed by the cerium-doped carbon-based Co electrocatalyst is about 4, which indicates that the cerium-doped carbon-based Co electrocatalyst is mainly based on 4 electron paths.
Fig. 7 is an XRD diffractogram of a series of cerium-doped carbon-based Co electrocatalysts, showing a diffraction peak of carbon at 26 ° and no diffraction peaks of Ce and Co, indicating that the particles of the metal element in the catalyst are small or exist in a monoatomic structure.

Claims (8)

1. A preparation method of a rare earth metal doped carbon-based oxygen reduction electrocatalyst is characterized by comprising the following steps: the method comprises the following steps:
firstly, putting a nitrogen source, a carbon source, a rare earth metal salt and a Fe/Co/Ni transition metal salt into a container, adding a solvent, sealing and heating to 40-80 ℃, stirring for 4-12h, adding formaldehyde, and continuously stirring for 10-16h to obtain a metal-organic complex precursor;
the rare earth metal salt comprises at least one of hydrated chlorides of lanthanum, cerium, neodymium, samarium, gadolinium, erbium and yttrium;
the Fe/Co/Ni transition metal salt comprises at least one of hydrated chlorides of Fe/Co/Ni;
secondly, transferring the metal-organic complex precursor obtained in the first step into a reaction container, and carrying out solvothermal reaction for 20-24h at the temperature of 100-200 ℃;
thirdly, placing the product obtained in the second step in a muffle furnace, and heating and oxidizing in air at the temperature of 150-;
fourthly, placing the product obtained in the third step into a tubular furnace, and carbonizing at the temperature of 800-1000 ℃ for 1-3h under the nitrogen atmosphere;
and fifthly, washing the carbonized product obtained in the fourth step by 0.5M sulfuric acid and deionized water to be neutral, and centrifugally drying to obtain the rare earth metal doped carbon-based oxygen reduction electrocatalyst.
2. The method of claim 1, wherein the rare earth metal doped carbon-based oxygen reduction electrocatalyst is prepared by the following steps: in the first step, the nitrogen source is a nitrogen-containing organic substance, and comprises at least one of melamine, urea, phenanthroline, dicyandiamide and bipyridine.
3. The method of claim 1, wherein the rare earth metal doped carbon-based oxygen reduction electrocatalyst is prepared by the following steps: in the first step, the carbon source is an aromatic compound containing carboxyl/aldehyde/amino/hydroxyl functional groups, and comprises at least one of 2, 4-dihydroxybenzoic acid, 2, 4-dihydroxybenzaldehyde, aminophenol, aminobenzoic acid, hydroxyquinoline, aminoquinoline, hydroxynaphthalene, aminonaphthalene, hydroxynaphthoic acid, aminonaphthoic acid, hydroxypyridine, carboxypyridine, hydroxypyrrole and carboxypyrrole.
4. The method of claim 1, wherein the rare earth metal doped carbon-based oxygen reduction electrocatalyst is prepared by the following steps: the solvent in the first step comprises at least one of water, ethanol and ethylene glycol.
5. The method of claim 1, wherein the rare earth metal doped carbon-based oxygen reduction electrocatalyst is prepared by the following steps: in the first step, the molar ratio of the Fe/Co/Ni transition metal salt to the rare earth metal salt to the carbon source to the nitrogen source to formaldehyde is 1: (0.1-0.5): (1-2): (2-5): (1-1).
6. The method of claim 1, wherein the rare earth metal doped carbon-based oxygen reduction electrocatalyst is prepared by the following steps: in the third step, the oxidation heating rate of the muffle furnace is 1-5 ℃/min.
7. The method of claim 1, wherein the rare earth metal doped carbon-based oxygen reduction electrocatalyst is prepared by the following steps: the carbonization temperature rise rate in the fourth step is 1-3 ℃/min.
8. A rare earth metal doped carbon-based oxygen reduction electrocatalyst prepared according to the preparation method of any one of claims 1 to 7.
CN202011417932.8A 2020-12-07 2020-12-07 Preparation method of rare earth metal doped carbon-based oxygen reduction electrocatalyst Active CN112563517B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011417932.8A CN112563517B (en) 2020-12-07 2020-12-07 Preparation method of rare earth metal doped carbon-based oxygen reduction electrocatalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011417932.8A CN112563517B (en) 2020-12-07 2020-12-07 Preparation method of rare earth metal doped carbon-based oxygen reduction electrocatalyst

Publications (2)

Publication Number Publication Date
CN112563517A CN112563517A (en) 2021-03-26
CN112563517B true CN112563517B (en) 2022-05-31

Family

ID=75059310

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011417932.8A Active CN112563517B (en) 2020-12-07 2020-12-07 Preparation method of rare earth metal doped carbon-based oxygen reduction electrocatalyst

Country Status (1)

Country Link
CN (1) CN112563517B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113699554B (en) * 2021-09-17 2022-11-15 中国矿业大学 Preparation method and application of rare earth metal and transition metal co-doped carbon-based material
TWI811822B (en) * 2021-10-26 2023-08-11 國立高雄科技大學 Cathode catalyst for metal-air battery and its preparation method
CN115364860A (en) * 2021-11-25 2022-11-22 浙江理工大学 Preparation method and application of iron-based flaky nano catalyst
CN116516410A (en) * 2023-05-10 2023-08-01 河南农业大学 Preparation method and application of biomass wood-based catalyst containing polymer

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120245019A1 (en) * 2011-03-23 2012-09-27 Brookhaven Science Associates, Llc Method and Electrochemical Cell for Synthesis of Electrocatalysts by Growing Metal Monolayers, or Bilayers and Treatment of Metal, Carbon, Oxide and Core-Shell Nanoparticles
CN108325565B (en) * 2018-02-01 2019-04-05 山西大学 Multi-functional carbon-based base metal elctro-catalyst of one kind and its preparation method and application
CN109802148A (en) * 2019-02-01 2019-05-24 上海亮仓能源科技有限公司 A kind of preparation method of on-vehicle fuel load type platinum rare earth metal cathod catalyst

Also Published As

Publication number Publication date
CN112563517A (en) 2021-03-26

Similar Documents

Publication Publication Date Title
CN112563517B (en) Preparation method of rare earth metal doped carbon-based oxygen reduction electrocatalyst
CN107020075B (en) Simple substance bismuth catalyst for electrochemical reduction of carbon dioxide and preparation and application thereof
CN111785977B (en) Preparation method of iron-cobalt alloy/nitrogen co-doped carbon aerogel electrocatalytic material
CN111430734B (en) (Pr0.5Sr0.5)xFe1-yRuyO3-δPerovskite material and preparation method and application thereof
CN113699554B (en) Preparation method and application of rare earth metal and transition metal co-doped carbon-based material
CN108336374B (en) High-performance ternary Fe-Co-Ni Co-doped nitrogen-containing carbon material and preparation method and application thereof
CN112058293B (en) Preparation method of nitrogen-phosphorus-codoped foam carbon nanosheet loaded NiCo nanoparticle composite material, product and application thereof
CN110729486A (en) Preparation method of elemental cobalt composite nitrogen-doped carbon high-efficiency oxygen reduction/oxygen precipitation catalyst
CN111041508A (en) Cobaltosic oxide array/titanium mesh water decomposition oxygen generation electrode and preparation method thereof
CN113322473B (en) Loaded Ni-CeO 2 Preparation method and application of heterojunction nitrogen-doped porous carbon nanofiber material
CN111450842B (en) Preparation method of micro-flower structure black lead-copper ore phase metal oxide electrocatalyst, electrocatalyst and application thereof
CN112553643A (en) Nitrogen-doped carbon-coated non-noble bimetallic cobalt-molybdenum oxide oxygen evolution reaction catalyst, preparation method and application
CN108786825B (en) Cerium dioxide-based nano electro-catalytic hydrogen evolution catalyst and preparation method thereof
CN113522368A (en) Fe and Co Co-doped sea urchin structure hollow carbon sphere electrocatalyst and preparation method thereof
CN115652357B (en) Sulfur-doped yttrium ruthenate, preparation method thereof and oxygen evolution reaction electrode
CN115739143B (en) Pt/alpha-MoC-CeO2Catalyst, preparation method thereof and application of catalyst in hydrogen production by methanol water vapor
CN113371687B (en) Porous heterostructure catalytic material and preparation method thereof
CN115786964B (en) Cobalt-based spinel Cu 0.7 Co 2.3 O 4 Electrocatalyst, preparation method and application thereof
CN114086196B (en) Oxygen evolution perovskite catalyst with low overpotential and high stability and preparation method thereof
CN114622240B (en) General preactivation method of anti-perovskite nitride, and product and application thereof
CN113224321B (en) Vanadium-doped carbon-coated iron carbide multifunctional composite electrocatalyst and preparation method and application thereof
CN113755888B (en) Novel Co@CoP2CF full-water electrolytic catalyst
CN115449823A (en) Application of perovskite type oxide surface in-situ desolventizing nano-copper catalyst in electrocatalytic carbon dioxide reduction
CN118531423A (en) R-P type perovskite solid oxide electrolytic cell cathode material with porous structure, and preparation method and application thereof
CN117154114A (en) Gd doped Co 3 O 4 Hollow microsphere electrocatalyst and preparation method 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