CN113136588A - Non-noble metal catalyst of nickel-doped iron-based bimetal and preparation method thereof - Google Patents

Non-noble metal catalyst of nickel-doped iron-based bimetal and preparation method thereof Download PDF

Info

Publication number
CN113136588A
CN113136588A CN202110354074.5A CN202110354074A CN113136588A CN 113136588 A CN113136588 A CN 113136588A CN 202110354074 A CN202110354074 A CN 202110354074A CN 113136588 A CN113136588 A CN 113136588A
Authority
CN
China
Prior art keywords
nickel
noble metal
catalyst
metal catalyst
chloride hexahydrate
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
CN202110354074.5A
Other languages
Chinese (zh)
Inventor
杨慧娟
张钰琳
王盛宝
严成
易小宇
郭智文
李倩
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.)
Xian University of Technology
Original Assignee
Xian University of Technology
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 Xian University of Technology filed Critical Xian University of Technology
Priority to CN202110354074.5A priority Critical patent/CN113136588A/en
Publication of CN113136588A publication Critical patent/CN113136588A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Landscapes

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

Abstract

The invention provides a nickel-doped iron-based bimetallic non-noble metal catalyst and a preparation method thereof. The non-noble metal-based catalyst takes SBA-15 as a hard template, sucrose as a carbon source, melamine as a nitrogen source, ferric chloride hexahydrate as an iron source and nickel chloride hexahydrate as a nickel source. And carrying out high-temperature carbonization treatment to obtain the FeNi/N-C catalyst. Compared with single metal Fe-N/C and Ni-N/C materials, the bimetallic FeNi-N/C material prepared by the invention plays a synergistic effect between Fe and Ni double metals and with a defective carbon material, so that the nickel-doped Fe-based bimetallic catalyst has high oxygen evolution performance and even exceeds commercial RuO2A catalyst. The non-noble metal oxygen evolution electrocatalyst prepared by the invention has the characteristics of low cost and high performance, and greatly promotes the commercialization process of an electrolytic hydrogen production system.

Description

Non-noble metal catalyst of nickel-doped iron-based bimetal and preparation method thereof
Technical Field
The invention belongs to the technical field of new materials, and relates to a nickel-doped iron-based bimetallic non-noble metal catalyst and a preparation method thereof.
Background
In order to solve the consumption of fossil fuel and environmental problems, the development of sustainable energy conversion and storage systems, such as reversible fuel cells, rechargeable metal air cells, and water electrolysis hydrogen production devices, is urgently required, however, these energy conversion and storage systems are restricted by the slow kinetic Oxygen Evolution Reaction (OER), and a high-efficiency and stable catalyst is required to accelerate the reaction. Currently, the industry is highly dependent on noble metal oxides RuO2And IrO2The catalyst is expensive and has poor stability, which seriously hinders the large-scale commercialization. This has therefore prompted a great deal of research effort directed towards the development of non-noble metal catalysts. In recent years, nickel-iron-based compounds have been receiving more and more attention due to their low cost and abundant content, and activity is greatly improved compared with single-metal Fe, Co and Ni-based catalysts reported separately based on excellent OER performance of nickel-iron-based catalysts. However, there are still many problems to be solved, such as insufficient active sites, low conductivity, and instability of the exposed metal in strong alkali, which makes the OER over-potential high, thereby affecting practical applications.
Disclosure of Invention
The invention aims to provide a nickel-doped iron-based bimetallic non-noble metal catalyst, which solves the problem of high overpotential of the non-noble metal catalyst in the oxygen evolution reaction in the prior art.
The invention also aims to provide a preparation method of the nickel-doped iron-based bimetallic non-noble metal catalyst, which solves the problem of high overpotential of the non-noble metal catalyst for oxygen evolution reaction in the prior art.
The first technical scheme adopted by the invention is that the nickel-doped iron-based bimetallic non-noble metal catalyst takes SBA-15 as a hard template, sucrose as a carbon source, melamine as a nitrogen source, ferric chloride hexahydrate as an iron source and nickel chloride hexahydrate as a nickel source.
The invention adopts another technical scheme that the preparation method of the nickel-doped iron-based bimetallic non-noble metal catalyst is used for preparing the nickel-doped iron-based bimetallic non-noble metal catalyst and is implemented according to the following steps:
step 1, mixing SBA-15, cane sugar and melamine, carbonizing by concentrated sulfuric acid, and drying to obtain a carbonized master batch;
step 2, adding cane sugar and melamine into the carbonized master batch obtained in the step 1 again, uniformly stirring, adding ferric chloride hexahydrate and nickel chloride hexahydrate, mixing, carbonizing again by concentrated sulfuric acid, uniformly stirring, putting into a drying oven, and drying to obtain a carbonized sub-material;
step 3, grinding the carbonized materials, putting the ground carbonized materials into a magnetic boat, and sintering the ground carbonized materials under the protection of nitrogen to obtain a catalyst base material;
and 4, pickling the catalyst base material with hydrofluoric acid, centrifuging, and drying at 50-60 ℃ to obtain the nickel-doped iron-based bimetallic non-noble metal catalyst.
The invention is also characterized in that:
the drying process in the step 1 and the drying process in the step 2 are carried out for 4-8 h at the temperature of 100-200 ℃ and 5-10 h at the temperature of 100-300 ℃.
The sintering process in the step 3 is that the sintering is carried out for 1 to 3 hours at the temperature of 200 to 400 ℃, and then the temperature is increased to 700 to 1000 ℃ for sintering for 0.5 to 2 hours.
The total mass ratio of the sucrose, the melamine and the ferric chloride hexahydrate added in the step 1 to the step 2 is 1-2: 2:1
The molar ratio of the ferric chloride hexahydrate and the nickel chloride hexahydrate added in the step 2 is 1: 1-2.
The invention has the beneficial effects that:
1. the non-noble metal catalyst of the nickel-doped iron-based bimetal prepared by the invention fully exerts the synergistic effect between the iron and the nickel bimetal and the defective carbon material, so that the catalyst has excellent oxygen evolution performance, and the overpotential is far lower than that of commercial RuO2。
2. The catalyst prepared by the invention is used as a catalyst of a water electrolysis hydrogen production system, has the advantages of high performance, low cost, simple operation and the like, and is expected to replace a noble metal-based catalyst.
Drawings
FIG. 1 is a diffraction pattern of a FeNi-N/C catalyst prepared in example 1 of the present invention;
FIG. 2 shows FeNi-N/C catalyst prepared in example 1 of the present invention and commercial RuO2Linear sweep voltammogram of the catalyst under basic conditions.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a nickel-doped iron-based bimetallic non-noble metal catalyst, which takes SBA-15 as a hard template, sucrose as a carbon source, melamine as a nitrogen source, ferric chloride hexahydrate as an iron source and nickel chloride hexahydrate as a nickel source.
A method for preparing a nickel-doped iron-based bimetallic non-noble metal catalyst adopts a hard template method to prepare the nickel-doped iron-based bimetallic non-noble metal catalyst, and is implemented according to the following steps:
step 1, mixing SBA-15, cane sugar and melamine, carbonizing by concentrated sulfuric acid, and drying to obtain a carbonized master batch;
step 2, adding cane sugar and melamine into the carbonized master batch obtained in the step 1 again, uniformly stirring, adding ferric chloride hexahydrate and nickel chloride hexahydrate, mixing, carbonizing again by concentrated sulfuric acid, uniformly stirring, putting into a drying oven, and drying to obtain a carbonized sub-material;
step 3, grinding the carbonized materials, putting the ground carbonized materials into a magnetic boat, and sintering the ground carbonized materials under the protection of nitrogen to obtain a catalyst base material;
and 4, pickling the catalyst base material with hydrofluoric acid, centrifuging, and drying at 50-60 ℃ to obtain the nickel-doped iron-based bimetallic non-noble metal catalyst.
The drying process in the step 1 and the drying process in the step 2 are carried out for 4-8 h at the temperature of 100-200 ℃ and 5-10 h at the temperature of 100-300 ℃.
The sintering process in the step 3 is that the sintering is carried out for 1 to 3 hours at the temperature of 200 to 400 ℃, and then the temperature is increased to 700 to 1000 ℃ for sintering for 0.5 to 2 hours.
The total mass ratio of the sucrose, the melamine and the ferric chloride hexahydrate added in the step 1 to the step 2 is 1-2: 2:1
The molar ratio of the ferric chloride hexahydrate and the nickel chloride hexahydrate added in the step 2 is 1: 1-2.
Example 1
Step 1, mixing 250mg SBA-15, 500mg sucrose and 1000mg melamine, carbonizing by 580 mu L concentrated sulfuric acid, then putting the mixture into a drying oven, drying for 4-8 h at the temperature of 100 ℃, and then drying for 5-10 h at the temperature of 160 ℃ to obtain a carbonized master batch;
step 2, adding 500mg of cane sugar and 1000mg of melamine into the carbonized master batch obtained in the step 1 again, uniformly stirring, adding 1mL of 1M ferric chloride hexahydrate and 1mL of 1M nickel chloride hexahydrate, mixing, carbonizing with 600 mu L of concentrated sulfuric acid again, uniformly stirring, putting into a drying oven, drying at the temperature of 100 ℃ for 6 hours, and drying at the temperature of 160 ℃ for 6 hours to obtain a carbonized sub-material;
step 3, grinding the carbonized materials, putting the ground carbonized materials into a magnetic boat, sintering the ground carbonized materials at the temperature of 300 ℃ for 1 hour under the protection of nitrogen, and then heating to 900 ℃ for sintering for 1 hour to obtain a catalyst base material;
and 4, pickling the catalyst base material with hydrofluoric acid, centrifuging, and drying at 50 ℃ to obtain the nickel-doped iron-based bimetallic non-noble metal catalyst.
It is measured by oxygen evolution linear sweep voltammetry under alkaline conditions at 10mA cm-2The overpotential at the current density of (2) is 320 mV.
The performance of the nickel-doped iron-based bimetallic non-noble metal catalyst prepared in example 1 of the present invention was tested.
Fig. 1 shows that when compared with a single-metal Fe-N/C material and a Ni-N/C material, the bimetallic catalyst shows diffraction peaks of fe0.64ni0.36 at positions of 43 °, 50 °, 74 ° respectively, indicating that the material contains iron and nickel elements, which proves that the non-noble metal catalyst of the nickel-doped iron-based bimetallic catalyst is successfully synthesized.
FIG. 2 shows the preparation of nickel-doped iron-based bimetallicNon-noble metal catalyst and commercial RuO2Linear sweep voltammogram with oxygen evolution under basic conditions. It can be seen from FIG. 1 that the RuO is comparable to commercial RuO2The catalyst has improved performance of phase oxygen evolution of FeNi-N/C catalyst, wherein the OER performance of the FeNi-N/C catalyst with Fe: Ni being 1:1 is very excellent. On the non-noble metal catalyst electrode prepared by the invention, the concentration is 10mA cm-2The initial potential and the overpotential at the current density are only 260mV and 320mV, which are respectively reduced by 140mV and 190mV compared with the initial potential (400mV) and the overpotential (510mV) of single Fe-N/C, while single Ni-N/C has almost no OER activity and is more than that of commercial RuO2The initial potential (290mV) and the overpotential (380mV) of the material are respectively lower by 30mV and 60mV, which indicates that the material is lower than the commercial RuO under alkaline conditions2Shows better oxygen evolution performance.
In summary, the non-noble metal catalyst of the nickel-doped iron-based bimetal prepared in embodiment 1 of the present invention exerts the synergistic effect between the iron-nickel duplex metal and the defective carbon material, for the FeNi-N/C material, the presence of iron and nickel metal species can significantly improve the conductivity of the electrocatalyst, accelerate the charge transfer to have better oxygen evolution catalytic performance, and the synergistic effect between Fe and Ni, and the NC layer and the metal phase can significantly improve the electrocatalytic activity for OER. The cost of the prepared catalyst is far lower than that of RuO2. Therefore, the catalyst used for the water electrolysis hydrogen production system has the characteristics of low cost, high performance and the like, and has important significance for large-scale commercial use.
Example 2
Step 1, mixing 250mgSBA-15, 1000mg sucrose and 1000mg melamine, carbonizing by 650 mu L concentrated sulfuric acid, then putting into a drying oven, drying at 150 ℃ for 7h before 1, and drying at 200 ℃ for 5h to obtain a carbonized master batch;
step 2, adding 1000mg of sucrose and 1000mg of melamine into the carbonized master batch obtained in the step 1 again, uniformly stirring, adding 0.5mL of 1M ferric chloride hexahydrate and 1mL of 1M nickel chloride hexahydrate, mixing, carbonizing again by using 700 mu L of concentrated sulfuric acid, uniformly stirring, putting into a drying oven, drying at 150 ℃ for 7h, and drying at 200 ℃ for 5h to obtain a carbonized sub-material;
step 3, grinding the carbonized materials, putting the ground carbonized materials into a magnetic boat, sintering the ground carbonized materials at the temperature of 250 ℃ for 1.5h under the protection of nitrogen, and then heating to 950 ℃ for sintering for 1.5h to obtain a catalyst base material;
and 4, pickling the catalyst base material with hydrofluoric acid, centrifuging, and drying at 60 ℃ to obtain the nickel-doped iron-based bimetallic non-noble metal catalyst.
Example 3
Step 1, mixing 250mgSBA-15, 1000mg sucrose and 1000mg melamine, carbonizing by using 500 mu L concentrated sulfuric acid, then putting the mixture into a drying oven, drying the mixture for 4 hours at the temperature of 100 ℃ before 1, and drying the mixture for 5 hours at the temperature of 100 ℃ to obtain carbonized master batch;
step 2, adding 1000mg of sucrose and 1000mg of melamine into the carbonized master batch obtained in the step 1 again, uniformly stirring, adding 0.5mL of 1M ferric chloride hexahydrate and 1mL of 1M nickel chloride hexahydrate, mixing, carbonizing again by 540 mu L of concentrated sulfuric acid, uniformly stirring, putting into a drying oven, drying at 100 ℃ for 4 hours, and drying at 100 ℃ for 5 hours to obtain a carbonized sub-material;
step 3, grinding the carbonized materials, putting the ground carbonized materials into a magnetic boat, sintering the ground carbonized materials at the temperature of 200 ℃ for 1 hour under the protection of nitrogen, and then heating to 700 ℃ for sintering for 0.5 hour to obtain a catalyst base material;
and 4, pickling the catalyst base material with hydrofluoric acid, centrifuging, and drying at 60 ℃ to obtain the nickel-doped iron-based bimetallic non-noble metal catalyst.
Example 4
Step 1, mixing 250mg SBA-15, 500mg cane sugar and 1000mg melamine, carbonizing by 700 mu L concentrated sulfuric acid, then putting the mixture into a drying oven, drying for 8h at 200 ℃, and then drying for 10h at 300 ℃ to obtain a carbonized master batch;
step 2, adding 500mg of cane sugar and 1000mg of melamine into the carbonized master batch obtained in the step 1 again, uniformly stirring, adding 1mL of 1M ferric chloride hexahydrate and 1mL of 1M nickel chloride hexahydrate, mixing, carbonizing with 500 mu L of concentrated sulfuric acid again, uniformly stirring, putting into a drying oven, drying at 200 ℃ for 8 hours, and drying at 300 ℃ for 10 hours to obtain a carbonized sub-material;
step 3, grinding the carbonized materials, putting the ground carbonized materials into a magnetic boat, sintering the ground carbonized materials at the temperature of 400 ℃ for 3 hours under the protection of nitrogen, and then heating to 1000 ℃ for sintering for 2 hours to obtain a catalyst base material;
and 4, pickling the catalyst base material with hydrofluoric acid, centrifuging, and drying at 55 ℃ to obtain the nickel-doped iron-based bimetallic non-noble metal catalyst.

Claims (6)

1. A nickel-doped iron-based bimetallic non-noble metal catalyst and a preparation method thereof are characterized in that the non-noble metal-based catalyst takes SBA-15 as a hard template, sucrose as a carbon source, melamine as a nitrogen source, ferric chloride hexahydrate as an iron source, and nickel chloride hexahydrate as a nickel source.
2. A method for preparing a non-noble metal catalyst of a nickel-doped iron-based bimetal, which is used for preparing the non-noble metal catalyst of the nickel-doped iron-based bimetal as claimed in claim 1, and is implemented by the following steps:
step 1, mixing SBA-15, cane sugar and melamine, carbonizing by concentrated sulfuric acid, and drying to obtain a carbonized master batch;
step 2, adding cane sugar and melamine into the carbonized master batch obtained in the step 1 again, uniformly stirring, adding ferric chloride hexahydrate and nickel chloride hexahydrate, mixing, carbonizing again by concentrated sulfuric acid, uniformly stirring, putting into a drying oven, and drying to obtain a carbonized sub-material;
step 3, grinding the carbonized materials, putting the ground carbonized materials into a magnetic boat, and sintering the ground carbonized materials under the protection of nitrogen to obtain a catalyst base material;
and 4, pickling the catalyst base material with hydrofluoric acid, centrifuging, and drying at 50-60 ℃ to obtain the nickel-doped iron-based bimetallic non-noble metal catalyst.
3. The method for preparing a nickel-doped iron-based bimetallic non-noble metal catalyst as claimed in claim 2, wherein the drying processes in the steps 1 and 2 are performed at 100-200 ℃ for 4-8 h, and then at 100-300 ℃ for 5-10 h.
4. The method for preparing a nickel-doped iron-based bimetallic non-noble metal catalyst as claimed in claim 2, wherein the sintering process in the step 3 is sintering at 200-400 ℃ for 1-3 h, and then heating to 700-1000 ℃ for sintering for 0.5-2 h.
5. The method for preparing the nickel-doped iron-based bimetallic non-noble metal catalyst as claimed in claim 2, wherein the total mass ratio of the sucrose, the melamine and the ferric chloride hexahydrate added in the step 1 to the step 2 is 1-2: 2: 1.
6. The method for preparing a nickel-doped iron-based bimetallic non-noble metal catalyst as claimed in claim 2, wherein the molar ratio of ferric chloride hexahydrate and nickel chloride hexahydrate added in step 2 is 1: 1-2.
CN202110354074.5A 2021-03-31 2021-03-31 Non-noble metal catalyst of nickel-doped iron-based bimetal and preparation method thereof Pending CN113136588A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110354074.5A CN113136588A (en) 2021-03-31 2021-03-31 Non-noble metal catalyst of nickel-doped iron-based bimetal and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110354074.5A CN113136588A (en) 2021-03-31 2021-03-31 Non-noble metal catalyst of nickel-doped iron-based bimetal and preparation method thereof

Publications (1)

Publication Number Publication Date
CN113136588A true CN113136588A (en) 2021-07-20

Family

ID=76810306

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110354074.5A Pending CN113136588A (en) 2021-03-31 2021-03-31 Non-noble metal catalyst of nickel-doped iron-based bimetal and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113136588A (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102671672A (en) * 2011-03-15 2012-09-19 中国科学院大连化学物理研究所 Preparation method and application of carbon-supported nickel-based catalyst
CN103055853A (en) * 2011-10-20 2013-04-24 中国科学院大连化学物理研究所 Method for preparation of water electrolysis oxygen evolution catalyst with silicon oxide molecular sieve as template
CN104201001A (en) * 2014-07-14 2014-12-10 上海应用技术学院 Rod-shaped nitrogen and phosphorus co-doping mesoporous carbon material and preparation method and application thereof
CN106882787A (en) * 2017-03-27 2017-06-23 华南理工大学 A kind of N doping ordered mesoporous carbon material and preparation method thereof
CN108855184A (en) * 2018-06-14 2018-11-23 中南大学 A kind of high-performance analysis oxygen CoO@Co-NC/C composite catalyst and its preparation method and application
CN111905794A (en) * 2020-08-24 2020-11-10 西安理工大学 High-density monatomic electrocatalyst and preparation method thereof
CN112058300A (en) * 2020-09-28 2020-12-11 西安理工大学 Non-noble metal catalyst carrying NiP quantum dots and preparation method and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102671672A (en) * 2011-03-15 2012-09-19 中国科学院大连化学物理研究所 Preparation method and application of carbon-supported nickel-based catalyst
CN103055853A (en) * 2011-10-20 2013-04-24 中国科学院大连化学物理研究所 Method for preparation of water electrolysis oxygen evolution catalyst with silicon oxide molecular sieve as template
CN104201001A (en) * 2014-07-14 2014-12-10 上海应用技术学院 Rod-shaped nitrogen and phosphorus co-doping mesoporous carbon material and preparation method and application thereof
CN106882787A (en) * 2017-03-27 2017-06-23 华南理工大学 A kind of N doping ordered mesoporous carbon material and preparation method thereof
CN108855184A (en) * 2018-06-14 2018-11-23 中南大学 A kind of high-performance analysis oxygen CoO@Co-NC/C composite catalyst and its preparation method and application
CN111905794A (en) * 2020-08-24 2020-11-10 西安理工大学 High-density monatomic electrocatalyst and preparation method thereof
CN112058300A (en) * 2020-09-28 2020-12-11 西安理工大学 Non-noble metal catalyst carrying NiP quantum dots and preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HE, X.等: ""Facile loading mesoporous Co3O4 on nitrogen doped carbon matrix as an enhanced oxygen electrode catalyst"", 《MATERIALS LETTERS》 *
LIN, QIN 等: ""Fe-doped Co-N/C as effective electrocatalyst for oxygen reaction"", 《MATERIALS RESEARCH EXPRESS》 *
王艺霖 等: ""铁镍合金纳米颗粒镶嵌的多级孔氮掺杂碳催化剂的制备及析氧性能研究"", 《化学学报》 *

Similar Documents

Publication Publication Date Title
CN109518219B (en) Preparation method and application of graphene-based nickel-cobalt bimetallic oxygen evolution catalyst
CN109569683B (en) Preparation method and application of nitrogen-phosphorus-codoped porous carbon sheet/transition metal phosphide composite material
CN110148762B (en) Carbon material with nitrogen, fluorine and transition metal co-doped graphene structure and one-step carbonization preparation method thereof
CN108579751B (en) Layered perovskite oxide, preparation method and application thereof in oxygen evolution reaction electrocatalysis
CN110813350B (en) Carbon-based composite electrocatalyst and preparation method and application thereof
CN112481653B (en) Defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst and preparation method and application thereof
CN111659439B (en) Nitrogen-doped carbon nano composite material loaded with NiS/NiO heterojunction and preparation method and application thereof
CN113388847A (en) Prussian blue analogue derived metal sulfide/nitrogen-doped carbon electrocatalyst and preparation method and application thereof
CN109759066B (en) Preparation method of boron-doped graphene-loaded cobalt-nickel bimetallic oxide oxygen evolution catalyst
CN113512737B (en) Nickel hydroxide electrocatalyst, preparation method, electrochemical activation method and application thereof
CN114628696B (en) Preparation method of porous carbon-supported cobalt-based bifunctional oxygen catalyst
CN113846343B (en) Preparation method of nickel molybdenum carbide electrocatalyst
CN114808018A (en) Monoatomic iron-doped nitrogen-carbon material and preparation method and application thereof
CN113201759B (en) Three-dimensional porous carbon supported bismuth sulfide/bismuth oxide composite catalyst and preparation method and application thereof
CN112002909B (en) Preparation method of Zn-Cu-N-based co-doped carbon composite material
CN114411195B (en) Nickel-manganese selenide heterojunction electrocatalyst and preparation method and application thereof
CN113668012B (en) Iron/ruthenium nitrogen-doped porous carbon electrocatalyst and preparation method and application thereof
CN112007671B (en) Fe1Co6-P @ CC electrocatalyst and preparation method thereof
CN112058300B (en) Non-noble metal catalyst carrying NiP quantum dots and preparation method and application thereof
CN113136588A (en) Non-noble metal catalyst of nickel-doped iron-based bimetal and preparation method thereof
CN114574891A (en) Preparation method and application of bimetallic co-doped nickel phosphide nanosheet
CN113774425A (en) Preparation method and application of Ru-modified FeCo @ NF electrocatalyst
CN112191242B (en) Use of oxide with hexagonal structure in oxygen evolution reaction
CN113644281A (en) Bimetal doped carbon composite material and preparation method and application thereof
CN114649538B (en) Electro-catalyst for preparing hydrogen by methanol electrolysis and preparation method 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
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20210720