CN110813350A - Carbon-based composite electrocatalyst and preparation method and application thereof - Google Patents
Carbon-based composite electrocatalyst and preparation method and application thereof Download PDFInfo
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000002135 nanosheet Substances 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 238000010992 reflux Methods 0.000 abstract description 2
- 230000004888 barrier function Effects 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 238000010668 complexation reaction Methods 0.000 abstract 1
- 239000007769 metal material Substances 0.000 abstract 1
- 229910052707 ruthenium Inorganic materials 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- -1 phosphides Chemical class 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
-
- 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
Abstract
The invention belongs to the field of electrocatalysts, and particularly relates to a preparation method and application of a high-performance carbon-based composite catalyst for electrochemically decomposing water to produce hydrogen. The Ru/NC electrocatalyst is prepared by using nitrogen-doped carbon (NC) synthesized through the processes of complexation, calcination and acid washing as a substrate material and ethylene glycol as a reducing agent under the reflux condition. The electro-catalyst material has lower charge transfer resistance and reaction barrier of hydrogen evolution reaction, and has excellent performance in the electro-catalytic hydrogen evolution reaction. Meanwhile, the catalyst has the advantages of low cost, simple and convenient experimental operation, simple process and excellent catalytic performance due to the lowest price of Ru in the Pt-series noble metal material, and provides basic application research for the material in the field of electrocatalysis.
Description
Technical Field
The invention belongs to the field of electrocatalysis, and particularly relates to a high-performance carbon-based composite electrocatalyst for electrochemically decomposing water to produce hydrogen, and a preparation method and application thereof.
Technical Field
With the continuous consumption of fossil fuels, various new energy production plans are receiving wide attention in order to meet the huge energy demand of the current. Hydrogen energy is a clean energy without any pollution and is expected to become the most effective substitute of fossil fuel. Hydrogen production (HER) by electrochemically decomposing water has the advantages of high efficiency, environmental friendliness, high hydrogen production purity, strong energy fluctuation adaptability and the like, and has great application prospect in the development of chemical energy storage technology.
Pt-based catalysts are still the most efficient HER catalysts at present, but their scarcity and high cost make them not widely applicable in industrial production applications. Thus, various non-platinum metal catalysts have been reported, mainly including transition metal oxides, carbides, nitrides, sulfides, selenides, phosphides, and hydroxides. However, these catalysts suffer from the disadvantages of poor stability and easy deactivation, and are not suitable for industrial application. Therefore, there is an urgent need to develop an electrocatalyst with high efficiency, long life and low cost. Among Pt noble metals, ruthenium (Ru) is the least expensive, and the composite of Ru and carbon is used as the catalyst for hydrogen production by water electrolysis, so that the catalyst has the advantages of moderate price, high hydrogen production efficiency, good circulation stability and the like. The nitrogen is doped into the carbon-based material, so that the electron donating performance of the carbon-based material can be improved, the dispersion of ruthenium particles is facilitated, and more active sites are easily exposed.
Scholars both at home and abroad have worked well in this regard. For example, Su et al, successfully synthesized a RuCo @ NC HER catalyst at a current density of 10mA cm-2And 100mA cm-2The overpotential is 28mV and 218mV respectively, and after 10000 CV stability tests, the overpotential is only increased by 4mV (Su J, Yang Y, Xia G, equivalent, Ruthenium-cobalt-aluminium encapsulated in nitro-gene-amplified graphene active electrolytes for producing hydrogen in alkalline media [ J ]]Naturecommunications,2017,8: 14969.). Successful synthesis of Ru @ C by Sun et al4N catalyst having excellent acidic and basic HER electrocatalytic activity. Under acidic conditions, the current density was 10mA cm-2The time overpotential is only 6mV, and the current density under alkaline condition is 10mA cm-2Time overpotential is only 7mV(Sun S W,Wang G F,Zhou Y,et al.High-Performance Ru@C4N Electrocatalyst for Hydrogen Evolution Reaction in BothAcidic and Alkaline Solutions[J].ACS applied materials&interfaces,2019.)。
Disclosure of Invention
The invention aims to provide a high-performance Ru/NC electrocatalyst for electrochemically decomposing water to produce hydrogen. The catalyst prepared by the method can greatly reduce the overpotential and the Tafel slope, has good conductivity, and can greatly improve the catalytic hydrogen production efficiency of the Ru-based catalyst for decomposing water. In addition, the Ru/NC synthesized in situ by taking NC as a substrate can reduce the internal resistance of the electrode, improve the conductivity of the electrode and obviously improve the catalytic activity of the material. Meanwhile, the catalyst cost can be greatly reduced by using cheap and easily-obtained nitrogen-doped carbon (NC) as a substrate material of the catalyst. Therefore, the Ru/NC electrocatalyst synthesized in situ by taking NC as a substrate material is applied to the field of hydrogen production by water electrolysis, and has better application prospect.
The technical scheme of the invention is as follows:
(1) preparation of nitrogen-doped carbon (NC):
a: weighing dopamine hydrochloride and FeCl3·6H2Grinding O in a mortar, transferring the reactant into a magnetic boat after the reactant is fully complexed, transferring the magnetic boat into an automatic program temperature control heating tube furnace, heating to 600-800 ℃ at a heating rate of 3-5 ℃/min, and calcining for 1-3 h; naturally cooling to room temperature, and taking out;
b: grinding the sample obtained in the step a, then placing the sample into an HCl solution, stirring, washing simple substance iron in the sample, then centrifuging, washing with water and alcohol, and drying to obtain an NC nanosheet;
(2) preparing an Ru/NC water electrolysis hydrogen production electrocatalyst with NC as a substrate:
a: weighing RuCl3To prepare RuCl3The ethylene glycol solution is reserved;
b: weighing the dried NC nanosheets obtained in the step (1), adding ethylene glycol for ultrasonic dispersion, and then adding the RuCl prepared in the step a3The ethylene glycol solution is uniformly dispersed, the solution is transferred into a round-bottom flask and is refluxed for 1 to 2 hours at the temperature of between 180 and 200 ℃; naturally cooling to room temperatureAnd then transferring the product to a centrifuge tube, washing with water and alcohol for several times, and drying to obtain the Ru/NC catalyst.
In the step a of the step (1), dopamine hydrochloride and FeCl3·6H2The molar ratio of O is 1: x, wherein x is 1-14.
In the step b of the step (1), the concentration of HCl is 1 mol/L.
In the step a of the step (2), RuCl3The concentration of the ethylene glycol solution is 5 mg/mL;
in the step b of the step (2), the concentration of NC in the glycol solution is 1-1.5 mg/mL, and NC nano-sheets and RuCl are added3The mass ratio of (1) to (x) is 1: x, wherein x is 0.1-0.5; preferably, x is 0.5.
In the steps (1) and (2), the drying temperature is 60 ℃, and the drying time is 12 hours.
The Ru/NC catalyst provided by the invention is applied to the aspect of electrocatalytic hydrogen production.
And (3) analyzing the composition morphology of the product by using an X-ray diffractometer (XRD) and a Transmission Electron Microscope (TEM). A three-electrode reaction device is adopted, a platinum wire is used as a counter electrode, a silver-silver chloride (Ag/AgCI) electrode is used as a reference electrode, and the electrochemical performance of the product is tested in 1MKOH electrolyte;
the invention has the beneficial effects that:
(1) the preparation method provided by the invention is composed of simple calcination reaction and reflux reaction, and has the advantages of simple steps, short reaction time, convenience in operation, environmental friendliness and strong repeatability.
(1) The Pt/C catalyst is still the most efficient electrocatalyst for hydrogen production by water electrolysis at present, but Ru used in the invention is used as the cheapest metal in Pt-series noble metals, the cost is less than 1/20 of Pt, but the electrocatalytic activity of Pt/C can be achieved, and the preparation cost of the catalyst is greatly reduced.
(3) The NC nanosheets provide an ultra-large specific surface area for the growth of the Ru simple substance, so that the particle size is effectively limited, and more active sites are exposed; and the good conductivity of the NC nanosheet is beneficial to electron transfer, and the factors synergistically enhance the electrocatalytic capacity of the material in a water decomposition reaction.
Drawings
FIG. 1 is an XRD diffraction spectrum of the prepared 20% Ru/NC nanosheet electrocatalyst and NC nanosheets.
FIGS. 2a, b, c are transmission photographs of the prepared pure NC nanosheet, 20% Ru/NC nanosheet, and 20% Ru/bulk NC electrocatalyst, respectively.
FIGS. 3a and b are a comparison graph of polarization curves and a comparison graph of overpotential values of hydrogen evolution reaction of the prepared electrocatalyst under the condition of 1M KOH, respectively.
FIG. 4 is a graph showing the comparison of the gradient of the Phillips curve of the prepared electrocatalyst in a hydrogen evolution reaction tower under the condition of 1M KOH.
FIG. 5 is a graph comparing the cycle stability of the prepared electrocatalyst CV after 3000 cycles.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
Example 1
Preparation of 20% Ru/NC nanosheet with NF as the substrate (meaning that Ru accounts for 20% of the total catalyst (NC + Ru) mass):
0.5689g dopamine hydrochloride and 5.6763g FeCl were weighed3·6H2Fully grinding the O in a mortar, transferring the complex into a magnetic boat, placing the magnetic boat in an automatic program temperature control heating tube furnace, heating to 700 ℃ at a heating rate of 5 ℃/min, and calcining for 2 h; and naturally cooling to room temperature, taking out, carrying out acid washing by using 1M HCl until no elemental iron exists, transferring to a centrifugal tube for centrifugation, and carrying out water washing and alcohol washing for several times to obtain the NC nanosheet.
100mg of the NC nanosheet prepared above was weighed into 65mL of ethylene glycol solution, and 10mL of RuCl was added3The solution (5mg/mL) was ultrasonically dispersed and refluxed at 190 ℃ for 1 hour. After naturally cooling to room temperature, centrifuging, washing with water and alcohol for several times, and drying at 60 ℃ for 12h, wherein the material is named as 20% Ru/NC nanosheet.
Example 2
The preparation of the electrocatalytic material was substantially the same as in example 1, except that no FeCl was added3·6H2O, no acid washing step is needed, and the material is named as 20% Ru/blocky NC。
Example 3
The preparation method of the electrocatalytic material is basically the same as that of the electrocatalytic material in example 1, except that 90mg of the NC nanosheet prepared in example 1 is weighed into 71mL of ethylene glycol solution, and 4mLRuCl is added3The material was named 10% Ru/NC nanosheet (meaning that Ru accounted for 10% of the total catalyst (NC + Ru) mass) in ethylene glycol solution (5 mg/mL).
Electrocatalytic activity test of Ru/NC electrode material
A KOH solution with the concentration of 1M is used as an electrolyte, a three-electrode reaction device is adopted, a Pt wire is used as a counter electrode, Ag/AgCI is used as a reference electrode, the scanning speed is 5mV/s, and the hydrogen production performance of electrocatalytic decomposition of water in the solution by the iron-doped nickel-cobalt double-metal phosphide electrode material is tested.
EXAMPLES characterization of Ru/NC catalysts
FIG. 1 is XRD diffraction spectra of the prepared 20% Ru/NC nanosheets and NC nanosheets, and it can be seen from the figures that no other impurities exist in the synthesized catalyst material.
FIGS. 2a, b, c are transmission electron micrographs of the prepared pure NC nanosheet, 20% Ru/NC nanosheet and 20% Ru/bulk NC electrocatalyst, respectively. As can be seen from the figure, with FeCl3·6H2And NC with the nanosheet shape can be obtained by adding O, so that the dispersion of Ru is facilitated.
FIGS. 3a and b are a comparison graph of polarization curves and a comparison graph of overpotential values of hydrogen evolution reaction of the prepared electrocatalyst under the condition of 1M KOH, respectively. From the figure, it can be analyzed that the HER activity of the 20% Ru/NC nanosheet electrocatalyst is not lower than that of the 20% Pt/C, and compared with pure Ru, the composite electrocatalyst shows more excellent point catalytic performance due to the synergistic effect between Ru particles and NC.
FIG. 4 is a graph showing the comparison of the gradient of the Phillips curve of the prepared electrocatalyst in a hydrogen evolution reaction tower under the condition of 1M KOH.
FIG. 5 is a graph comparing the cycling stability of 20% Ru/NC nanosheet electrocatalyst CV after 3000 cycles. It can be seen that the activity of the catalyst before and after the cycle did not differ much.
Claims (8)
1. A preparation method of a carbon-based composite electrocatalyst is characterized by comprising the following steps:
(1) preparation of nitrogen-doped carbon (NC):
a: weighing dopamine hydrochloride and FeCl3·6H2Grinding O in a mortar, transferring the reactant into a magnetic boat after the reactant is fully complexed, transferring the magnetic boat into an automatic program temperature control heating tube furnace, heating to 600-900 ℃ at a heating rate of 3-5 ℃/min, and calcining for 1-3 h; naturally cooling to room temperature, and taking out;
b: grinding the sample obtained in the step a, then placing the sample in an HCl solution for stirring, centrifuging after the simple substance iron in the sample is cleaned, washing with water and alcohol, and drying to obtain NC;
(2) preparing a Ru/NC water electrolysis hydrogen production catalyst with NC as a substrate:
a: weighing RuCl3To prepare RuCl3The ethylene glycol solution is reserved;
b: weighing the dried NC obtained in the step (1), adding ethylene glycol for ultrasonic dispersion, and then adding the RuCl prepared in the step a3The ethylene glycol solution is uniformly dispersed, the solution is transferred into a round-bottom flask and is refluxed for 1 to 2 hours at the temperature of between 180 and 200 ℃; and naturally cooling to room temperature, transferring to a centrifuge tube, washing with water and alcohol for several times, and drying to obtain the carbon-based composite electrocatalyst.
2. The method of preparing a carbon-based composite electrocatalyst according to claim 1, wherein: in the step a of the step (1), dopamine hydrochloride and FeCl3·6H2The molar ratio of O is 1: x, wherein x is 1-14.
3. The method of claim 1, wherein the carbon-based composite catalyst comprises: in the step b of the step (1), the concentration of HCl is 1 mol/L.
4. The method of preparing a carbon-based composite electrocatalyst according to claim 1, wherein: in the step a of the step (2), RuCl3The concentration of the ethylene glycol solution of (2) was 5 mg/mL.
5. The method of preparing a carbon-based composite electrocatalyst according to claim 1, wherein: in the step b of the step (2), the concentration of NC in the glycol solution is 1-1.5 mg/mL, and NC nano-sheets and RuCl are added3The mass ratio of (a) to (b) is 1: x, wherein x is 0.1-0.5.
6. The method of preparing a carbon-based composite electrocatalyst according to claim 5, wherein: in the step b of the step (2), NC nanosheet and RuCl3In the mass ratio of (a) to (b) of 1: x, wherein x is 0.5.
7. The method of preparing a carbon-based composite electrocatalyst according to claim 1, wherein: in the steps (1) and (2), the drying temperature is 60 ℃, and the drying time is 12 hours.
8. Use of the carbon-based composite electrocatalyst prepared by the preparation method according to any one of claims 1 to 7, characterized in that the carbon-based composite electrocatalyst is used for hydrogen production by electrocatalytic decomposition of water under alkaline conditions.
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| CN111468163A (en) * | 2020-05-12 | 2020-07-31 | 大连理工大学 | Two-dimensional iron monatomic catalyst, preparation thereof and application thereof in reduction production of ethylene by 1, 2-dichloroethane |
| CN111905725A (en) * | 2020-08-25 | 2020-11-10 | 浙江工业大学 | Ru-based catalyst and preparation method and application thereof |
| CN112680741A (en) * | 2021-01-12 | 2021-04-20 | 江苏大学 | Preparation method and application of ruthenium-doped cobalt phosphide electrocatalyst |
| CN113186559A (en) * | 2021-04-30 | 2021-07-30 | 西北有色金属研究院 | Preparation method of amorphous tantalum pentoxide supported ruthenium electrocatalyst |
| CN113667995A (en) * | 2021-08-24 | 2021-11-19 | 西北工业大学深圳研究院 | Two-dimensional flaky dopamine pyrolytic carbon-coated ruthenium nanocluster catalyst and preparation and use method thereof |
| CN114540863A (en) * | 2022-01-14 | 2022-05-27 | 辽宁华融富瑞新能源科技股份有限公司 | Preparation method of ruthenium-loaded nitrogen-doped porous carbon hydrogen evolution electrocatalyst |
| CN115364884A (en) * | 2021-11-12 | 2022-11-22 | 福州大学 | Preparation method of ruthenium-based catalyst and application of ruthenium-based catalyst in mild ammonia synthesis |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106040277A (en) * | 2016-06-08 | 2016-10-26 | 复旦大学 | Pt-supported carbon fiber composite adopting 'vesica string' structure and preparation method of carbon fiber composite |
| CN108039500A (en) * | 2017-12-25 | 2018-05-15 | 济南大学 | A kind of preparation method of iron nitrogen codope carbon nanometer micro ball and oxygen reduction application |
| CN108736028A (en) * | 2018-05-31 | 2018-11-02 | 深圳大学 | A kind of porous nitrogen-doped carbon Supported Co nano material, preparation method and applications |
| CN108807906A (en) * | 2018-06-12 | 2018-11-13 | 河南师范大学 | A kind of preparation method of nitrogen-doped carbon cladding classification through-hole structure ferroferric oxide composite cathode material |
| CN108889331A (en) * | 2018-08-10 | 2018-11-27 | 运城学院 | A kind of electrocatalytic hydrogen evolution material and preparation method thereof |
| CN109449379A (en) * | 2018-09-12 | 2019-03-08 | 华南师范大学 | A kind of SnFe that nitrogen-doped carbon is compound2O4Lithium ion battery negative material and the preparation method and application thereof |
-
2019
- 2019-10-25 CN CN201911020471.8A patent/CN110813350B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106040277A (en) * | 2016-06-08 | 2016-10-26 | 复旦大学 | Pt-supported carbon fiber composite adopting 'vesica string' structure and preparation method of carbon fiber composite |
| CN108039500A (en) * | 2017-12-25 | 2018-05-15 | 济南大学 | A kind of preparation method of iron nitrogen codope carbon nanometer micro ball and oxygen reduction application |
| CN108736028A (en) * | 2018-05-31 | 2018-11-02 | 深圳大学 | A kind of porous nitrogen-doped carbon Supported Co nano material, preparation method and applications |
| CN108807906A (en) * | 2018-06-12 | 2018-11-13 | 河南师范大学 | A kind of preparation method of nitrogen-doped carbon cladding classification through-hole structure ferroferric oxide composite cathode material |
| CN108889331A (en) * | 2018-08-10 | 2018-11-27 | 运城学院 | A kind of electrocatalytic hydrogen evolution material and preparation method thereof |
| CN109449379A (en) * | 2018-09-12 | 2019-03-08 | 华南师范大学 | A kind of SnFe that nitrogen-doped carbon is compound2O4Lithium ion battery negative material and the preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| YI PENG等: ""Hydrogen evolution reaction catalyzed by ruthenium ion-complexed graphitic carbon nitride nanosheets"", 《J. MATER. CHEM. A》 * |
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