CN114214661A - Composite material of ultrathin hydrotalcite nanosheet coupled metal and nitrogen co-doped porous carbon array and preparation method and application thereof - Google Patents

Composite material of ultrathin hydrotalcite nanosheet coupled metal and nitrogen co-doped porous carbon array and preparation method and application thereof Download PDF

Info

Publication number
CN114214661A
CN114214661A CN202111535609.5A CN202111535609A CN114214661A CN 114214661 A CN114214661 A CN 114214661A CN 202111535609 A CN202111535609 A CN 202111535609A CN 114214661 A CN114214661 A CN 114214661A
Authority
CN
China
Prior art keywords
metal
electrode
metal salt
nitrogen
solution
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.)
Granted
Application number
CN202111535609.5A
Other languages
Chinese (zh)
Other versions
CN114214661B (en
Inventor
沈葵
郭通天
李映伟
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.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
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 South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN202111535609.5A priority Critical patent/CN114214661B/en
Publication of CN114214661A publication Critical patent/CN114214661A/en
Application granted granted Critical
Publication of CN114214661B publication Critical patent/CN114214661B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • 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)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

The invention discloses a composite material of ultrathin hydrotalcite (LDHs for short) nanosheet coupled Metal and nitrogen co-doped porous carbon array (Metal-NC for short) and a preparation method and application thereof. Preparing Metal salt and organic ligand solution, putting the Metal salt and the organic ligand solution into a conductive substrate, standing, washing and drying to obtain a Metal-ZIF-L material; pyrolyzing a Metal-ZIF-L material in an inert atmosphere to obtain a Metal-NC material; adding the Metal-NC material into a deionized water solution of Metal salt, performing electrodeposition, washing and drying to obtain the Metal-NC @ LDHs material. The method provided by the invention is simple and safe, the thickness of the obtained LDHs is below 2nm, and meanwhile, the material has the advantages of high specific surface area, good structural firmness, good conductivity, high charge transfer speed, excellent catalytic activity in reactions such as water electrolysis and the like, and good application prospect.

Description

Composite material of ultrathin hydrotalcite nanosheet coupled metal and nitrogen co-doped porous carbon array and preparation method and application thereof
Technical Field
The invention belongs to the field of preparation of hydrotalcite (LDHs) composite materials, and particularly relates to an ultrathin hydrotalcite nanosheet coupled metal and nitrogen co-doped porous carbon array composite material, and a preparation method and application thereof.
Background
In response to increasing energy demand and associated environmental crisis, hydrogen gas productionHas attracted worldwide attention as a clean energy source with high energy density and reproducibility. For the production of hydrogen, electrolyzed water is considered a promising technology due to its high efficiency and environmental friendliness (w.j.jiang, t.tang, y.zhang, j.s.hu, acc.chem.res.,2020,53, 1111.). Electrocatalytic hydrolysis mainly involves two electrode reactions, the cathodic Hydrogen Evolution Reaction (HER) and the anodic Oxygen Evolution Reaction (OER). Currently, noble metal-containing platinum-carbon (Pt/C) and ruthenium dioxide (RuO)2) And iridium dioxide (IrO)2) Are considered to be the most effective HER and OER catalysts, respectively. However, their scarcity, high cost and instability hinder their further applications (y.p.zhu, c.guo, y.zheng, s.z.qiao, acc.chem.res.2017,50,915.). Therefore, the preparation of the double-functional hydrolysis electrocatalyst with high activity, good stability and low cost is urgently needed.
Layered Double Hydroxides (LDHs) refer to compounds with Layered structure, interlayer ions and exchangeability, and are formed by orderly assembling main body laminates with positive charges and interlayer anions through non-covalent interaction, wherein the main body laminates are formed by MO6Octahedron are formed by sharing edges. LDHs have many excellent properties (e.g., exchangeability of interlayer anions, controllability of composition and structure, memory effect, thermal stability, etc.) which other conventional materials do not have, and thus show great potential applications in the fields of ion exchange and adsorption, medicine, catalysis, etc. (a.i. khan, d.o 'Hare, j.mater.chem.2002,12,3191; q.wang, d.o' Hare, chem.rev.2012,112,7, 4124-4155). Especially in the aspect of electrocatalytic oxygen evolution, the material is the electrocatalytic material most likely to replace noble metal base due to the characteristics of low cost and high activity. However, the LDHs still face many problems in practical application. Firstly, in the actual process of preparing and applying the electrode material, the dispersed two-dimensional sheet structure is easy to agglomerate, thereby greatly reducing the catalytic activity of the electrode material. Secondly, the thickness of the LDHs prepared by the conventional method is large, which limits the exposure of active sites thereof, thereby reducing the intrinsic activity thereof (j.yu, q.wang, d.o' Hare, l.sun, chem.soc.rev.2017,46,5950.). Due to the fact thatThus, the preparation of ultra-thin LDH materials with more coordinately unsaturated active sites has become a valuable study. Generally, ultra-thin LDH materials are mainly prepared by two ways, one is top-down exfoliation including solvent exfoliation and plasma etching etc. and the other is bottom-up synthesis mainly including an interlayer growth inhibitor method and a microemulsion method (y.wang, y.zhang, z.liu, c.xie, s.feng, d.liu, m.sho, s.wang, angelw.chem.int.ed.2017, 56,5867; y.zhao, x.zhang, x.jia, g.i.n.waters, r.shi, x.r.zhang, f.zhan, y.tao, l.z.wu, c.h.tung, d.o' Hare, t.zhang, adv.energy mater.2018,8,1703585; l.lv, z.wu, wang.k.wang, wang.20152, energy, x.r.r.zhang, r.t.r.r.t.t.r.r.t.r.t.r.r.zhang, t.t.t.t.t.t.t.r.t.t.r.t.t.r.t.r.t.r.r.t.r.r.t.r.t.t.t.r.r.t.t.t.t.t.t.r.t.t.r.t.t.t.t.t.r.r.t.t.r.r.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.r.r.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.r.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t. However, both methods generally suffer from high time and economic costs, and high toxicity of the additives. Electrochemical deposition is currently considered to be a fast, efficient and environmentally friendly method for preparing LDH materials. It can not only fix LDHs on the substrate, but also control the size by adjusting the condition of electrodeposition. However, to date, the preparation of ultra-thin LDH nanosheets having a thickness of less than 2nm by this method has been little investigated. Meanwhile, in order to improve the electrocatalytic hydrogen evolution activity, the structure of the catalyst is usually damaged by further treatment such as phosphorization and sulfuration, so that the stability in the catalytic process is reduced. Therefore, in order to further improve the performance of the existing LDHs materials in electrocatalytic hydrolysis, the above-mentioned bottleneck problem must be overcome.
Disclosure of Invention
The invention provides a preparation method of an ultrathin hydrotalcite nanosheet coupled metal and nitrogen co-doped porous carbon array supported by a conductive substrate, aiming at the problems that an LDH powder material is large in thickness and easy to agglomerate and stack in application in the traditional preparation process. According to the method, the LDHs nanosheets rich in oxygen vacancies with different types and thicknesses can be obtained by adjusting the composition of the electrolyte and the electrodeposition time. Meanwhile, the method is simple and safe, and the obtained product has the advantages of high specific surface area, good structural firmness, good conductivity, high charge transfer speed, excellent catalytic activity in reactions such as water electrolysis and the like, and good application prospect.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a composite material of an ultrathin hydrotalcite nanosheet coupled metal and nitrogen co-doped porous carbon array comprises the following steps:
(1) adding an organic ligand into deionized water, and performing ultrasonic dispersion and dissolution to obtain an organic ligand solution; dissolving a metal salt in deionized water, and performing ultrasonic dispersion to obtain a metal salt solution;
(2) adding the Metal salt solution obtained in the step (1) into an organic ligand solution, uniformly mixing, then putting into a conductive substrate, standing, washing and drying to obtain a Metal-ZIF-L material;
(3) pyrolyzing the Metal-ZIF-L material in the step (2) in an inert atmosphere to obtain a Metal-NC material;
(4) and (4) adding the Metal-NC material obtained in the step (3) into a deionized water solution of Metal salt, performing electrodeposition, washing and drying to obtain the Metal-NC @ LDHs material.
Preferably, the metal salt in step (1) is one or more of nitrate, chloride and acetate of cobalt, zinc, nickel, copper and iron;
preferably, the organic ligand in the step (1) is 2-methylimidazole;
preferably, the molar ratio of the organic ligand to the metal salt in the step (2) is (0.5-16): 1.
preferably, the conductive substrate in the step (2) is any one of carbon cloth, carbon paper, foamed nickel, foamed iron, foamed copper and copper foil;
preferably, the conductive substrate in the step (2) is vertically placed into the mixed solution;
preferably, the standing time in the step (2) is 0.1-48 h.
Preferably, the inert atmosphere in the step (3) is nitrogen or argon;
preferably, the pyrolysis temperature in the step (3) is 300-1100 ℃, and the pyrolysis time is 0.1-48 h.
Preferably, the metal salt in step (4) is one or more of nitrate, chloride and acetate of cobalt, zinc, cerium, nickel, copper, iron, manganese and magnesium;
preferably, the concentration of the metal salt in the deionized water solution of the metal salt in the step (4) is 0.01-8 mol/L.
Preferably, the electrodeposition in the step (3) adopts a three-electrode system, which comprises a reference electrode, a counter electrode and a working electrode clamp.
Further preferably, the reference electrode is Ag/AgCl, Hg/Hg2Cl2And one of Hg/HgO electrode, the counter electrode is one of carbon rod, platinum sheet and platinum wire, and the working electrode clamp is one of Pt and glassy carbon electrode clamps.
Preferably, the voltage of the electrodeposition in the step (4) is-15 to-0.01V, and the time of the electrodeposition is 10 to 1000 s.
The ultrathin hydrotalcite nanosheet coupled metal and nitrogen-codoped porous carbon array composite material prepared by the preparation method has the advantages that the type of hydrotalcite in the ultrathin hydrotalcite nanosheet coupled metal and nitrogen-codoped porous carbon array composite material is adjustable, the thickness is 0.5-60 nm, and the composite material has abundant oxygen vacancies. The material has a three-dimensional multi-level sheet structure, and the type and thickness of LDH nano sheets on the material can be adjusted according to the composition of a metal salt solution and the electrodeposition time.
The composite material of the ultrathin hydrotalcite nanosheet coupled metal and nitrogen co-doped porous carbon array is applied to catalytic hydrogen production.
Compared with the prior art, the invention has the following advantages:
(1) the Metal-NC @ LDHs material prepared by the invention can ensure that the prepared ultrathin LDH nanosheet has rich oxygen vacancies, the type and thickness of the LDH nanosheet are adjustable, the thickness of the LDH nanosheet can be controlled below 2nm by changing the electrodeposition time, and the thickness of the LDH nanosheet prepared by electrodeposition, which is reported in the literature and patents at present, is generally above 2 nm.
(2) The preparation process is simple, safe and controllable, and environment-friendly, and the most important thing is that the prepared Metal-NC @ LDHs material has high catalytic activity when being used for electrocatalytic hydrolysis, and can reach 10mA cm under the voltage of 1.55V-2And the current density can be stably operated for more than 40 h.
Drawings
FIG. 1 shows Co-NC @ Ni with three-dimensional multi-level nano-sheet structure prepared in example 14 of the present invention2Scanning electron micrographs of Fe-LDH material.
FIG. 2 shows Co-NC @ Ni with three-dimensional multi-level nano-sheet structure prepared in example 14 of the present invention2And (3) a transmission electron microscope photo of the Fe-LDH material.
FIG. 3 shows Ni grown on the surface of Co-NC prepared in example 14 of the present invention2And (3) atomic force microscope photos of the Fe-LDH nanosheets.
FIG. 4 shows Ni grown on the surface of Co-NC prepared in example 14 of the present invention2And (3) an electron paramagnetic resonance spectrogram of the Fe-LDH nanosheet.
FIG. 5 is a Co-NC microarray of example 1, Co-NC @ Ni with three-dimensional multi-level nano-platelet structure prepared in example 14, according to the present invention2Fe-LDH Material and Ni of example 192And (3) a catalytic performance evaluation diagram of the Fe-LDHs material on the electrocatalytic hydrolysis reaction.
FIG. 6 shows Co-NC @ Ni with three-dimensional multi-level nano-sheet structure prepared in example 14 of the present invention2And (3) a stability performance evaluation chart of the Fe-LDH material on the electrocatalytic hydrolysis reaction.
Detailed Description
Specific embodiments of the present invention will be described in further detail below with reference to the drawings and examples, but the present invention is not limited thereto.
Example 1
1.314g of 2-methylimidazole, 0.586g of Co (NO)3)2·6H2And O is respectively added into 40mL deionized water solution and dissolved by ultrasonic for 5 min. Then adding the obtained cobalt nitrate solution into the 2-methylimidazole solution for uniform mixing. The carbon cloth was then placed vertically into the mixed solution and allowed to stand at room temperature for 4 h. And washing the obtained carbon cloth with the color changed into purple, and drying in an oven at 60 ℃ for 24 h. And (3) paving the dried sample in a quartz boat, putting the quartz boat in a tube furnace for pyrolysis, wherein the pyrolysis atmosphere is nitrogen, and pyrolyzing the sample for 3 hours at 600 ℃ at the heating rate of 1 ℃/min to obtain the sample, namely the leaf-shaped Co-NC micron array.
Example 2
1.314g of 2-methylimidazole and 0.465g of Co (NO)3)2·6H2O and 0.149g Ni (NO)3)2·6H2And O is respectively added into 40mL deionized water solution and dissolved by ultrasonic for 5 min. And then adding the obtained mixed solution of cobalt nitrate and nickel nitrate into the 2-methylimidazole solution for uniform mixing. The carbon cloth was then placed vertically into the mixed solution and allowed to stand at room temperature for 4 h. And washing the obtained carbon cloth with the color changed into purple, and drying in an oven at 60 ℃ for 24 h. And (3) paving the dried sample in a quartz boat, putting the quartz boat in a tube furnace for pyrolysis, wherein the pyrolysis atmosphere is nitrogen, and pyrolyzing the sample for 3h at 600 ℃ at the heating rate of 1 ℃/min to obtain the sample, namely the leaf-shaped CoNi-NC micron array.
Example 3
1.314g of 2-methylimidazole and 0.465g of Co (NO)3)2·6H2O and 0.207g Fe (NO)3)3·9H2And O is respectively added into 40mL deionized water solution and dissolved by ultrasonic for 5 min. And then adding the obtained mixed solution of cobalt nitrate and ferric nitrate into the 2-methylimidazole solution for uniform mixing. The carbon cloth was then placed vertically into the mixed solution and allowed to stand at room temperature for 4 h. And washing the obtained carbon cloth with the color changed into purple, and drying in an oven at 60 ℃ for 24 h. And (3) paving the dried sample in a quartz boat, putting the quartz boat in a tube furnace for pyrolysis, wherein the pyrolysis atmosphere is nitrogen, and pyrolyzing the sample for 3h at 600 ℃ at the heating rate of 1 ℃/min to obtain the sample, namely the leaf-shaped CoFe-NC micron array.
Example 4
1.314g of 2-methylimidazole and 0.465g of Co (NO)3)2·6H2O and 0.096g Cu (NO)3)3·6H2And O is respectively added into 40mL deionized water solution and dissolved by ultrasonic for 5 min. And then adding the obtained mixed solution of cobalt nitrate and copper nitrate into the 2-methylimidazole solution for uniform mixing. The carbon cloth was then placed vertically into the mixed solution and allowed to stand at room temperature for 4 h. And washing the obtained carbon cloth with the color changed into purple, and drying in an oven at 60 ℃ for 24 h. Spreading the dried sample in quartz boat, putting in tube furnace for pyrolysis, and adding pyrolysis gasAnd (3) pyrolyzing the mixture for 3 hours at 600 ℃ at the temperature rise rate of 1 ℃/min in the atmosphere of nitrogen to obtain a sample, namely the leaf-shaped CoCu-NC micron array.
Example 5
1.314g of 2-methylimidazole, 0.586g of Co (NO)3)2·6H2And O is respectively added into 40mL deionized water solution and dissolved by ultrasonic for 5 min. Then adding the obtained cobalt nitrate solution into the 2-methylimidazole solution for uniform mixing. The nickel foam was then placed vertically into the mixed solution and allowed to stand at room temperature for 4 h. And washing the obtained foam nickel with the color changed into purple, and then drying in an oven at 60 ℃ for 24 h. And (3) paving the dried sample in a quartz boat, putting the quartz boat in a tube furnace for pyrolysis, wherein the pyrolysis atmosphere is nitrogen, and pyrolyzing the sample for 3 hours at 600 ℃ at the heating rate of 1 ℃/min to obtain the sample, namely the leaf-shaped Co-NC micron array.
Example 6
1.314g of 2-methylimidazole, 0.586g of Co (NO)3)2·6H2And O is respectively added into 40mL deionized water solution and dissolved by ultrasonic for 5 min. Then adding the obtained cobalt nitrate solution into the 2-methylimidazole solution for uniform mixing. The iron foam was then placed vertically into the mixed solution and allowed to stand at room temperature for 4 h. And washing the obtained foam iron with the color changed into purple, and drying in an oven at 60 ℃ for 24 h. And (3) paving the dried sample in a quartz boat, putting the quartz boat in a tube furnace for pyrolysis, wherein the pyrolysis atmosphere is nitrogen, and pyrolyzing the sample for 3 hours at 600 ℃ at the heating rate of 1 ℃/min to obtain the sample, namely the leaf-shaped Co-NC micron array.
Example 7
1.314g of 2-methylimidazole, 0.586g of Co (NO)3)2·6H2And O is respectively added into 40mL deionized water solution and dissolved by ultrasonic for 5 min. Then adding the obtained cobalt nitrate solution into the 2-methylimidazole solution for uniform mixing. The copper foil was then placed vertically into the mixed solution and allowed to stand at room temperature for 4 h. And washing the obtained copper foil with the color changed into purple, and then drying in an oven at 60 ℃ for 24 h. Spreading the dried sample in quartz boat, pyrolyzing in tubular furnace in nitrogen atmosphere at 600 deg.C at 1 deg.C/minAnd (5) solving for 3h to obtain a sample, namely the foliated Co-NC micron array.
Example 8
Taking 2X 3cm2The carbon cloth of example 1 was sandwiched between a Pt electrode holder as the working electrode, an Ag/AgCl electrode as the reference electrode, and a carbon rod as the working electrode, all placed in Ni (NO)3)2·6H2O (0.218g) and Fe (NO)3)3·9H2O (0.303g) in a mixed solution (50mL) of deionized water. In a three-electrode system, the applied voltage was-0.9V vs. SCE, and the electrodeposition time was 50 s. And after the deposition is finished, washing the carbon cloth, and drying the carbon cloth in an oven at 60 ℃ for 24h to obtain a sample, namely the Co-NC @ NiFe-LDH material with the three-dimensional multi-stage nano sheet structure, wherein the thickness of the LDH nano sheet on the Co-NC @ NiFe-LDH material is about 0.8 nm.
Example 9
Taking 2X 3cm2The carbon cloth of example 1 was sandwiched between a Pt electrode holder as the working electrode, an Ag/AgCl electrode as the reference electrode, and a carbon rod as the working electrode, all placed in Ni (NO)3)2·6H2O (0.218g) and Fe (NO)3)3·9H2O (0.303g) in a mixed solution (50mL) of deionized water. In a three-electrode system, the applied voltage is-0.9V vs. SCE, and the electrodeposition time is 100 s. And after the deposition is finished, washing the carbon cloth, and drying the carbon cloth in an oven at 60 ℃ for 24h to obtain a sample, namely the Co-NC @ NiFe-LDH material with the three-dimensional multi-stage nano sheet structure, wherein the thickness of the LDH nano sheet on the Co-NC @ NiFe-LDH material is about 1.1 nm.
Example 10
Taking 2X 3cm2The carbon cloth of example 1 was sandwiched between a Pt electrode holder as the working electrode, an Ag/AgCl electrode as the reference electrode, and a carbon rod as the working electrode, all placed in Ni (NO)3)2·6H2O (0.218g) and Fe (NO)3)3·9H2O (0.303g) in a mixed solution (50mL) of deionized water. In a three-electrode system, the applied voltage was-0.9V vs. SCE, and the electrodeposition time was 150 s. After deposition is finished, the carbon cloth is washed clean, and is put into an oven at 60 ℃ for drying for 24h to obtain a sample, namely the Co-NC @ NiFe-LDH material with a three-dimensional multistage nano sheet structure, and LDH nano on the Co-NC @ NiFe-LDH materialThe thickness of the sheet was about 1.5 nm.
Example 11
Taking 2X 3cm2The carbon cloth of example 1 was sandwiched between a Pt electrode holder as the working electrode, an Ag/AgCl electrode as the reference electrode, and a carbon rod as the working electrode, all placed in Ni (NO)3)2·6H2O (0.218g) and Fe (NO)3)3·9H2O (0.303g) in a mixed solution (50mL) of deionized water. In a three-electrode system, the applied voltage is-0.9V vs. SCE, and the electrodeposition time is 200 s. And after the deposition is finished, washing the carbon cloth, and drying the carbon cloth in an oven at 60 ℃ for 24h to obtain a sample, namely the Co-NC @ NiFe-LDH material with the three-dimensional multi-stage nano sheet structure, wherein the thickness of the LDH nano sheet on the Co-NC @ NiFe-LDH material is about 1.9 nm.
Example 12
Taking 2X 3cm2The carbon cloth of example 1 was sandwiched between a Pt electrode holder as the working electrode, an Ag/AgCl electrode as the reference electrode, and a carbon rod as the working electrode, all placed in Ni (NO)3)2·6H2O (0.218g) and Fe (NO)3)3·9H2O (0.303g) in a mixed solution (50mL) of deionized water. In a three-electrode system, the applied voltage is-0.9V vs. SCE, and the electrodeposition time is 300 s. And after the deposition is finished, washing the carbon cloth, and drying the carbon cloth in an oven at 60 ℃ for 24h to obtain a sample, namely the Co-NC @ NiFe-LDH material with the three-dimensional multi-stage nano sheet structure, wherein the thickness of the LDH nano sheet on the Co-NC @ NiFe-LDH material is about 6.0 nm.
Example 13
Taking 2X 3cm2The carbon cloth of example 1 was sandwiched between a Pt electrode holder as the working electrode, an Ag/AgCl electrode as the reference electrode, and a carbon rod as the working electrode, all placed in Ni (NO)3)2·6H2O (0.145g) and Fe (NO)3)3·9H2O (0.404g) in a mixed solution (50mL) of deionized water. In a three-electrode system, the applied voltage is-0.9V vs. SCE, and the electrodeposition time is 200 s. After deposition is finished, the carbon cloth is washed clean and is put into an oven at 60 ℃ for drying for 24h, and the obtained sample is Co-NC @ NiFe with the three-dimensional multistage nano flaky structure2LDH material, LDH nanosheets thereon having a thickness of about 1.9nm。
Example 14
Taking 2X 3cm2The carbon cloth of example 1 was sandwiched between a Pt electrode holder as the working electrode, an Ag/AgCl electrode as the reference electrode, and a carbon rod as the working electrode, all placed in Ni (NO)3)2·6H2O (0.290g) and Fe (NO)3)3·9H2O (0.202g) in a mixed solution (50mL) of deionized water. In a three-electrode system, the applied voltage is-0.9V vs. SCE, and the electrodeposition time is 200 s. After deposition is finished, the carbon cloth is washed clean and is put into an oven at 60 ℃ for drying for 24h, and the obtained sample is Co-NC @ Ni with a three-dimensional multistage nano flaky structure2The thickness of the LDH nano sheet on the Fe-LDHs material is about 1.9 nm.
FIG. 1 shows Co-NC @ Ni with three-dimensional multi-level nano-sheet structure prepared in this example2SEM (scanning electron microscope) picture of Fe-LDHs material can see ultrathin Ni2Fe-LDH nanosheets are uniformly and vertically deposited on the foliated Co-NC precursor to form a typical core-shell structure; FIG. 2 shows the Co-NC @ Ni2TEM (Transmission Electron microscope photograph) of Fe-LDHs material can more clearly see Co nanoparticles uniformly distributed in Co-NC and ultrathin LDH nanosheet structure on the surface of Co nanoparticles, and further confirm the core-shell structure thereof, and FIG. 3 shows Ni grown on the surface of Co-NC2AFM (atomic force microscope) photographs of Fe-LDH nanosheets revealed a thickness of about 1.9 nm; FIG. 4 shows Ni grown on the surface of Co-NC2An EPR (electron paramagnetic resonance) spectrogram of the Fe-LDH nanosheet can show that a huge signal peak exists at a position where g is 2.003, which indicates that the Fe-LDH nanosheet contains a large number of oxygen vacancies; FIG. 5 is a graph showing the evaluation of the catalytic performance of the sample on the electrocatalytic hydrolysis reaction (reaction conditions: 1X 1 cm)2The catalyst, 5mv/s scanning speed, 85% compensation, 50mL of KOH (1M) aqueous solution as electrolyte) can be seen to reach 10mA cm at a voltage of 1.55V-2And the voltage of the Co-NC microarray is 1.70V. FIG. 6 is a graph showing the stability evaluation of the sample for the electrocatalytic hydrolysis reaction, and it can be seen that the catalyst can stably operate for more than 40 hours. Structure and method of Metal-NC @ LDHs prepared in other embodimentsThe catalytic performance test was substantially similar to the present example.
Example 15
Taking 2X 3cm2The carbon cloth of example 1 was sandwiched between Pt electrode clamps as the working electrode, an Ag/AgCl electrode as the reference electrode, and a carbon rod as the working electrode, all placed in Co (NO)3)2·6H2O (0.218g) and Fe (NO)3)3·9H2O (0.303g) in a mixed solution (50mL) of deionized water. In a three-electrode system, the applied voltage is-0.9V vs. SCE, and the electrodeposition time is 200 s. And after the deposition is finished, washing the carbon cloth, and drying the carbon cloth in an oven at 60 ℃ for 24h to obtain a sample, namely the Co-NC @ CoFe-LDH material with the three-dimensional multistage nano sheet structure, wherein the thickness of the LDH nano sheet on the Co-NC @ CoFe-LDH material is about 1.8 nm. The obtained material is applied to electrocatalytic hydrolysis at 10mA cm-2The voltage at the current density of (1.64V).
Example 16
Taking 2X 3cm2The carbon cloth of example 1 was sandwiched between Pt electrode clamps as the working electrode, an Ag/AgCl electrode as the reference electrode, and a carbon rod as the working electrode, all placed in Co (NO)3)2·6H2O (0.218g) and Ni (NO)3)2·6H2O (0.218g) in a mixed solution (50mL) of deionized water. In a three-electrode system, the applied voltage is-0.9V vs. SCE, and the electrodeposition time is 200 s. And after the deposition is finished, washing the carbon cloth, and drying the carbon cloth in an oven at 60 ℃ for 24h to obtain a sample, namely the Co-NC @ CoNi-LDH material with the three-dimensional multistage nano sheet structure, wherein the thickness of the LDH nano sheet on the Co-NC @ CoNi-LDH material is about 1.7 nm. The obtained material is applied to electrocatalytic hydrolysis at 10mA cm-2The voltage at the current density of (1.78) V.
Example 17
Taking 2X 3cm2The carbon cloth of example 1 was sandwiched between Pt electrode clamps as the working electrode, an Ag/AgCl electrode as the reference electrode, and a carbon rod as the working electrode, all placed in Zn (NO)3)2·6H2O (0.222g) and Fe (NO)3)3·9H2O (0.303g) in a mixed solution (50mL) of deionized water. Under a three-electrode system, the applied voltage is-0.9V vs. SCE, and the electrodeposition time is 200 s. And after the deposition is finished, washing the carbon cloth, and drying the carbon cloth in an oven at 60 ℃ for 24h to obtain a sample, namely the Co-NC @ ZnFe-LDH material with the three-dimensional multistage nano sheet structure, wherein the thickness of the LDH nanosheet on the Co-NC @ ZnFe-LDH material is about 1.8 nm. The obtained material is applied to electrocatalytic hydrolysis at 10mA cm-2The voltage at the current density of (1.70V).
Example 18
Taking 2X 3cm2The carbon cloth of example 1 was sandwiched between Pt electrode clamps as the working electrode, an Ag/AgCl electrode as the reference electrode, a carbon rod as the working electrode, all placed over MgSO4·7H2O (0.185g) and Fe (NO)3)3·9H2O (0.303g) in a mixed solution (50mL) of deionized water. In a three-electrode system, the applied voltage is-0.9V vs. SCE, and the electrodeposition time is 200 s. And after the deposition is finished, washing the carbon cloth, and drying the carbon cloth in an oven at 60 ℃ for 24h to obtain a sample, namely the Co-NC @ MgFe-LDH material with the three-dimensional multistage nano sheet structure, wherein the thickness of the LDH nano sheet on the Co-NC @ MgFe-LDH material is about 1.7 nm. The obtained material is applied to electrocatalytic hydrolysis at 10mA cm-2The voltage at the current density of (2) was 1.74V.
Example 19
Taking 2X 3cm2Carbon cloth without Co-NC material is clamped on Pt electrode clamp as working electrode, Ag/AgCl electrode as reference electrode, carbon rod as working electrode, and Ni (NO) is arranged3)2·6H2O (0.290g) and Fe (NO)3)3·9H2O (0.202g) in a mixed solution (50mL) of deionized water. In a three-electrode system, the applied voltage is-0.9V vs. SCE, and the electrodeposition time is 200 s. After deposition is finished, the carbon cloth is washed clean and put into an oven at 60 ℃ for drying for 24h, and the obtained sample is Ni with the nano flaky structure2The thickness of the LDH nano sheets on the Fe-LDHs material is about 22 nm.
The above-described embodiments are intended to illustrate rather than to limit the invention, and any modifications and variations of the present invention are within the spirit of the invention and the scope of the appended claims.

Claims (10)

1. A preparation method of a composite material of an ultrathin hydrotalcite nanosheet coupled metal and nitrogen co-doped porous carbon array is characterized by comprising the following steps:
(1) adding an organic ligand into deionized water to obtain an organic ligand solution; dissolving a metal salt in deionized water to obtain a metal salt solution;
(2) adding the Metal salt solution obtained in the step (1) into an organic ligand solution, uniformly mixing, then putting into a conductive substrate, standing, washing and drying to obtain a Metal-ZIF-L material;
(3) pyrolyzing the Metal-ZIF-L material in the step (2) in an inert atmosphere to obtain a Metal-NC material;
(4) and (4) adding the Metal-NC material obtained in the step (3) into a deionized water solution of Metal salt, performing electrodeposition, washing and drying to obtain the Metal-NC @ LDHs material.
2. The preparation method according to claim 1, wherein the metal salt in step (1) is one or more of nitrate, chloride and acetate of cobalt, zinc, nickel, copper and iron; the organic ligand is 2-methylimidazole;
the molar ratio of the organic ligand to the metal salt in the step (2) is (0.5-16): 1.
3. the method according to claim 1, wherein the conductive substrate of step (2) is any one of carbon cloth, carbon paper, nickel foam, iron foam, copper foam, and copper foil; vertically putting the mixed solution into the conductive substrate;
and (3) standing for 0.1-48 h.
4. The method according to claim 1, wherein the inert atmosphere in the step (3) is nitrogen or argon; the pyrolysis temperature is 300-1100 ℃, and the pyrolysis time is 0.1-48 h.
5. The method according to claim 1, wherein the metal salt in step (4) is one or more of nitrate, chloride and acetate of cobalt, zinc, cerium, nickel, copper, iron, manganese and magnesium;
and (4) the concentration of the metal salt in the deionized water solution of the metal salt is 0.01-8 mol/L.
6. The method of claim 1, wherein the electrodeposition employs a three-electrode system comprising a reference electrode, a counter electrode, and a working electrode holder.
7. The method according to claim 6, wherein the reference electrode is Ag/AgCl, Hg/Hg2Cl2And one of Hg/HgO electrode, the counter electrode is one of carbon rod, platinum sheet and platinum wire, and the working electrode clamp is one of Pt and glassy carbon electrode clamps.
8. The method according to claim 1, wherein the voltage of the electrodeposition in the step (4) is-15V to-0.01V, and the time of the electrodeposition is 10 s to 1000 s.
9. The composite material of the ultrathin hydrotalcite nanosheet coupled metal and nitrogen-codoped porous carbon array prepared by the preparation method of any one of claims 1 to 8, wherein the thickness of the hydrotalcite nanosheet in the composite material of the ultrathin hydrotalcite nanosheet coupled metal and nitrogen-codoped porous carbon array is 0.5-60 nm.
10. The application of the composite material of the ultrathin hydrotalcite nanosheet coupled metal and nitrogen co-doped porous carbon array of claim 9 in catalytic hydrogen production.
CN202111535609.5A 2021-12-15 2021-12-15 Ultrathin hydrotalcite nanosheet coupled metal and nitrogen co-doped porous carbon array composite material and preparation method and application thereof Active CN114214661B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111535609.5A CN114214661B (en) 2021-12-15 2021-12-15 Ultrathin hydrotalcite nanosheet coupled metal and nitrogen co-doped porous carbon array composite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111535609.5A CN114214661B (en) 2021-12-15 2021-12-15 Ultrathin hydrotalcite nanosheet coupled metal and nitrogen co-doped porous carbon array composite material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114214661A true CN114214661A (en) 2022-03-22
CN114214661B CN114214661B (en) 2023-06-20

Family

ID=80702541

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111535609.5A Active CN114214661B (en) 2021-12-15 2021-12-15 Ultrathin hydrotalcite nanosheet coupled metal and nitrogen co-doped porous carbon array composite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114214661B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115445624A (en) * 2022-10-10 2022-12-09 上海纳米技术及应用国家工程研究中心有限公司 Preparation method and application of ZIF (zinc oxide fluoride) self-templated layered multi-metal hydroxide electrocatalyst
CN115505949A (en) * 2022-08-31 2022-12-23 武汉工程大学 Iridium-doped metal organic framework derivative material, preparation method thereof and application of iridium-doped metal organic framework derivative material in aspect of electrocatalytic oxygen evolution

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107381658A (en) * 2017-07-12 2017-11-24 北京化工大学 A kind of topological preparation method of ultra-thin porous two-dimensional layer transition metal oxide nano-slice array material
CN111889117A (en) * 2020-08-08 2020-11-06 青岛科技大学 Core-shell copper selenide @ nickel iron hydrotalcite electrocatalyst, preparation method thereof and application of electrocatalyst in water electrolysis

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107381658A (en) * 2017-07-12 2017-11-24 北京化工大学 A kind of topological preparation method of ultra-thin porous two-dimensional layer transition metal oxide nano-slice array material
CN111889117A (en) * 2020-08-08 2020-11-06 青岛科技大学 Core-shell copper selenide @ nickel iron hydrotalcite electrocatalyst, preparation method thereof and application of electrocatalyst in water electrolysis

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DANDAN LI ET AL.: "Highly efficient Ni nanotube arrays and Ni nanotube arrays coupled with NiFe layered-double-hydroxide electrocatalysts for overall water splitting", 《JOURNAL OF POWER SOURCES》 *
DI CHEN ET AL.: "Dual-active-site Hierarchical Architecture Containing NiFe-LDH and ZIFderived Carbon-based Framework Composite as Efficient Bifunctional Oxygen Electrocatalysts for Durable Rechargeable Zn-Air Batteries", 《CHEMICAL ENGINEERING JOURNAL》 *
HAIDONG YANG ET AL.: "In-situ Growth of Ultrathin Ni-Fe LDHs Nanosheets for High Performance Oxygen Evolution Reaction", 《THE ROYAL SOCIETY OF CHEMISTRY》 *
HONGYUN QI ET AL.: "Cu2Se nanowires shelled with NiFe layered double hydroxide nanosheets for overall water-splitting", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115505949A (en) * 2022-08-31 2022-12-23 武汉工程大学 Iridium-doped metal organic framework derivative material, preparation method thereof and application of iridium-doped metal organic framework derivative material in aspect of electrocatalytic oxygen evolution
CN115445624A (en) * 2022-10-10 2022-12-09 上海纳米技术及应用国家工程研究中心有限公司 Preparation method and application of ZIF (zinc oxide fluoride) self-templated layered multi-metal hydroxide electrocatalyst

Also Published As

Publication number Publication date
CN114214661B (en) 2023-06-20

Similar Documents

Publication Publication Date Title
Zhao et al. Rhodium phosphide ultrathin nanosheets for hydrazine oxidation boosted electrochemical water splitting
Qiu et al. Highly exposed ruthenium-based electrocatalysts from bimetallic metal-organic frameworks for overall water splitting
CN114214661B (en) Ultrathin hydrotalcite nanosheet coupled metal and nitrogen co-doped porous carbon array composite material and preparation method and application thereof
Jin et al. Self-supported CoFe LDH/Co 0.85 Se nanosheet arrays as efficient electrocatalysts for the oxygen evolution reaction
CN109371420B (en) Single-layer porous nickel-iron hydrotalcite-based electrocatalytic oxygen evolution electrode and preparation method and application thereof
CN111483999B (en) Preparation method of nitrogen-doped carbon nanotube, nitrogen-doped carbon nanotube and application of nitrogen-doped carbon nanotube
CN110639534A (en) Oxygen evolution electrocatalytic material and preparation method and application thereof
CN106824189B (en) A kind of preparation method and its usage of ruthenium-molybdenum dioxide nano junction
CN111701607A (en) MnCo2O4@Ni2P/NF difunctional full-hydrolysis catalyst and preparation method and application thereof
CN114540831A (en) Nickel-iron bimetal coordination polymer catalyst for water electrolysis and preparation method thereof
CN110565113B (en) Preparation method of composite electrocatalytic material for alkaline electrocatalytic hydrogen evolution
CN113529122B (en) Nickel-organic framework nano-sheet array material and preparation method and application thereof
CN110681407A (en) Fe doped Co1.11Te2@ NCNTFs nano composite material and preparation method thereof
Sfirloaga et al. Addressing electrocatalytic activity of metal-substituted lanthanum manganite for the hydrogen evolution reaction
CN117107286A (en) Batch preparation method of NiFe-based composite oxygen evolution anode
CN115557469B (en) Amorphous noble metal oxide material and preparation method and application thereof
CN114774983B (en) Ultra-small Ru nanocluster supported on MoO 3-x Double-function composite material of nano belt and preparation method and application thereof
CN114381758B (en) Nickel-doped boehmite and reduced graphene oxide composite electrocatalyst and preparation and application thereof
CN110624607A (en) In-situ grown two-dimensional conductive metal organic compound array
CN113463119B (en) Bismuth-based-silver-based composite material and preparation method and application thereof
CN113897637B (en) Efficient atomic-level tungsten dispersion catalyst preparation method, product and application thereof
CN114888298A (en) Two-dimensional high-entropy alloy and preparation method and application thereof
Xu et al. Hydrothermal synthesis of Co3O4 nanowire electrocatalysts for oxygen evolution reaction
CN110420649B (en) Metal phase MoS2-CoNi(OH)2Nano composite material and preparation method and application thereof
CN114214636B (en) Method for preparing cobalt-based nanosheet self-supporting electrode by selenium-containing ligand and application of cobalt-based nanosheet self-supporting electrode

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