CN114214661B - Ultrathin hydrotalcite nanosheet coupled metal and nitrogen co-doped porous carbon array composite material and preparation method and application thereof - Google Patents

Ultrathin hydrotalcite nanosheet coupled metal and nitrogen co-doped porous carbon array composite material and preparation method and application thereof Download PDF

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CN114214661B
CN114214661B CN202111535609.5A CN202111535609A CN114214661B CN 114214661 B CN114214661 B CN 114214661B CN 202111535609 A CN202111535609 A CN 202111535609A CN 114214661 B CN114214661 B CN 114214661B
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沈葵
郭通天
李映伟
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South China University of Technology SCUT
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    • 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

Abstract

The invention discloses a composite material of ultrathin hydrotalcite (LDHs) nanosheet coupling Metal and nitrogen co-doped porous carbon array (Metal-NC) and a preparation method and application thereof. The Metal-ZIF-L material is prepared by preparing Metal salt and organic ligand solution, placing the Metal salt and the organic ligand solution into a conductive substrate, standing, washing and drying; pyrolyzing the Metal-ZIF-L material in an inert atmosphere to obtain a Metal-NC material; and adding the Metal-NC material into 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, meanwhile, the material has high specific surface area, good structural firmness, good conductivity and high charge mass transfer speed, and the LDHs has excellent catalytic activity in reactions such as water electrolysis and the like and has good application prospect.

Description

Ultrathin hydrotalcite nanosheet coupled metal and nitrogen co-doped porous carbon array composite material 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 a composite material of ultrathin hydrotalcite nano-sheet coupling metal and nitrogen co-doped porous carbon arrays, and a preparation method and application thereof.
Background
To cope with the increasing energy demands and the associated environmental crisis, hydrogen has attracted worldwide attention as a clean energy source with high energy density and renewable. For the production and manufacture of hydrogen, electrolyzed water is considered a promising technology because of 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, cathodic Hydrogen Evolution (HER) and anodic Oxygen Evolution (OER), respectively. 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 have hindered their further use (Y.P.Zhu, C.Guo, Y.Zheng, S.Z.Qiao, acc.Chem.Res.2017,50,915.). Therefore, there is an urgent need for preparing a hydrolysis electrocatalyst with dual functions that has high activity, good stability, and low cost.
Layered double hydroxide (Layered Double Hydroxides, LDHs) is a compound with layered structure, interlayer ion and exchangeable property, and is composed of positively charged main laminate and interlayer anion sequentially assembled by non-covalent bond interactionThe body layer plate is made of MO 6 Octahedra share edges. LDHs have many other excellent properties (e.g., interchangeability of interlayer anions, regulatory feasibility of composition and structure, memory effect and thermal stability, etc.) that conventional materials do not possess, 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). Particularly in the aspect of electrocatalytic oxygen evolution, the electrocatalytic material has become the most likely alternative to noble metal based electrocatalytic materials at present due to the characteristics of low cost and high activity. However, LDHs materials still face many problems in practical applications. Firstly, in the actual preparation and application process of the electrode material, the dispersed two-dimensional lamellar structure of the electrode material is easy to agglomerate, so that the catalytic activity of the electrode material is greatly reduced. Secondly, the greater thickness of LDHs prepared using conventional methods limits their active site exposure, thereby reducing their intrinsic activity (J.Yu, Q.Wang, D.O' Hare, L.Sun, chem.Soc.Rev.2017,46,5950.). Thus, the preparation of ultrathin LDH materials with more coordinated unsaturated active sites is a valuable study. In general, ultrathin LDH materials are mainly prepared in two ways, one from top to bottom, including solvent stripping and plasma etching, etc., and the other from bottom to top, mainly including interlayer growth inhibitor methods and microemulsion methods (Y.Wang, Y.Zhang, Z.Liu, C.Xie, S.Feng, D.Liu, M.Shao, S.Wang, angew.Chem.Int.Ed.2017,56,5867;Y.Zhao,X.Zhang,X.Jia,G.I.N.Waterhouse,R.Shi,X.R.Zhang,F.Zhan,Y.Tao,L.—z.wu, c.—h.tune, d.o' Hare, T.Zhang, adv.Energy mate.2018, 8,1703585;L.Lv,Z.Yang,K.Chen,C.Wang,Y.Xiong,Adv.Energy Mater.2019,9,1803358.). However, both of these 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 of 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, few studies have been made to produce ultrathin LDH nanoplatelets with a thickness of less than 2nm by this method. At the same time, in order to improve the electrocatalytic hydrogen evolution activityOften, further phosphating, sulfiding, etc. treatments are required, which can damage the structure and thus reduce stability during catalysis. Therefore, in order to further improve the performance of the existing LDHs materials in terms of electrocatalytic hydrolysis, the bottleneck problem described above must be overcome.
Disclosure of Invention
Aiming at the problems that the LDH powder material in the traditional preparation process has larger thickness and is easy to agglomerate and stack during application, the invention provides a preparation method of an ultrathin hydrotalcite nanosheet coupling metal and nitrogen co-doped porous carbon array supported by a conductive substrate. The method can obtain LDHs nano-sheets rich in oxygen vacancies with different types and thicknesses by adjusting the composition of the electrolyte and the electrodeposition time. Meanwhile, the method is simple and safe, the obtained product has high specific surface area, good structural firmness, good conductivity and high charge mass transfer speed, and the product has excellent catalytic activity in reactions such as water electrolysis and the like and has good application prospect.
The aim of the invention is realized by the following technical scheme:
a preparation method of a composite material of ultrathin hydrotalcite nanosheet coupling 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 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 placing 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 (3) adding the Metal-NC material in the step (3) into deionized water solution of Metal salt, performing electrodeposition, washing and drying to obtain the Metal-NC@LDHs material.
Preferably, the metal salt in the step (1) is one or more of nitrate, chloride and acetate of cobalt, zinc, nickel, copper and iron;
preferably, the organic ligand of 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, foam nickel, foam iron, foam copper and copper foil;
preferably, the conductive substrate in the step (2) is vertically placed into the mixed solution;
preferably, the time of standing 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 the 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 of step (3) employs a three electrode system comprising a reference electrode, a counter electrode and a working electrode clamp.
Further preferably, the reference electrode is Ag/AgCl, hg/Hg 2 Cl 2 And any one of Hg/HgO electrodes, wherein the counter electrode is any one of a carbon rod, a platinum sheet or a platinum wire, and the working electrode clamp is any one of a Pt or glassy carbon electrode clamp.
Preferably, the voltage of the electrodeposition in the step (4) is-15 to-0.01V, and the electrodeposition time is 10 to 1000s.
The ultra-thin hydrotalcite nano sheet coupled metal and nitrogen co-doped porous carbon array composite material prepared by the preparation method has adjustable hydrotalcite types, thickness of 0.5-60 nm and abundant oxygen vacancies. The material has a three-dimensional multi-stage lamellar structure, and the types and thickness of LDH nano sheets on the material can be adjusted according to the composition of the metal salt solution and the electrodeposition time.
The ultra-thin hydrotalcite nano-sheet coupled metal and nitrogen co-doped porous carbon array composite material 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 method can ensure that the prepared ultrathin LDH nanosheets have abundant oxygen vacancies, the types and the thickness of the ultrathin LDH nanosheets are adjustable, the thickness of the ultrathin LDH nanosheets can be controlled below 2nm by changing the electrodeposition time, and the thickness of the LDH nanosheets prepared by electrodeposition reported in the current literature and patents is generally above 2nm.
(2) The preparation process is simple, safe and controllable, is environment-friendly, and most importantly, the prepared Metal-NC@LDHs material has very high catalytic activity when being used for electrocatalytic hydrolysis, and can reach 10mA cm under the voltage of 1.55V -2 And can stably operate for more than 40 hours.
Drawings
FIG. 1 is a schematic diagram of Co-NC@Ni having a three-dimensional multi-stage nano-platelet structure prepared in example 14 of the invention 2 Scanning electron microscope photographs of Fe-LDH material.
FIG. 2 is a schematic diagram of Co-NC@Ni having a three-dimensional multi-stage nano-platelet structure prepared in example 14 of the invention 2 Transmission electron micrograph of Fe-LDH material.
FIG. 3 is a Co-NC surface-grown Ni prepared in example 14 of the present invention 2 Atomic force microscope photograph of Fe-LDH nanoplatelets.
FIG. 4 shows the Co-NC surface-grown Ni prepared in example 14 of the present invention 2 Electron paramagnetic resonance spectrogram of the Fe-LDH nanoplatelets.
FIG. 5 shows a Co-NC@Ni array of example 1, prepared in example 14, of the present invention having a three-dimensional multi-stage nanoplatelet structure 2 Fe-LDH Material and Ni of example 19 2 And a catalytic performance evaluation graph of Fe-LDHs materials on electrocatalytic hydrolysis reaction.
FIG. 6 is a Co-NC@Ni film having a three-dimensional multi-stage nano-platelet structure prepared in example 14 of the present invention 2 Fe-LDH materialStability performance evaluation graph for 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 embodiments of the present invention are not limited thereto.
Example 1
1.314g of 2-methylimidazole, 0.586g of Co (NO 3 ) 2 ·6H 2 O is added into 40mL deionized water solution respectively, and dissolved by ultrasonic treatment for 5 min. And then adding the obtained cobalt nitrate solution into the 2-methylimidazole solution, and uniformly mixing. The carbon cloth was then placed vertically into the mixed solution and allowed to stand at room temperature for 4 hours. And washing the obtained carbon cloth with the purple color, and then putting the carbon cloth into a 60 ℃ oven for drying for 24 hours. Spreading the dried sample in a quartz boat, placing in a tube furnace for pyrolysis, wherein the pyrolysis atmosphere is nitrogen, and pyrolyzing for 3 hours at 600 ℃ at the heating rate of 1 ℃/min to obtain the sample, namely the leaf-shaped Co-NC micro-array.
Example 2
1.314g of 2-methylimidazole, 0.465g of Co (NO) 3 ) 2 ·6H 2 O and 0.149g Ni (NO) 3 ) 2 ·6H 2 O is added into 40mL deionized water solution respectively, and dissolved by ultrasonic treatment for 5 min. And then adding the obtained mixed solution of cobalt nitrate and nickel nitrate into the 2-methylimidazole solution, and uniformly mixing. The carbon cloth was then placed vertically into the mixed solution and allowed to stand at room temperature for 4 hours. And washing the obtained carbon cloth with the purple color, and then putting the carbon cloth into a 60 ℃ oven for drying for 24 hours. Spreading the dried sample in a quartz boat, placing in a tube furnace for pyrolysis, wherein the pyrolysis atmosphere is nitrogen, and pyrolyzing for 3 hours at 600 ℃ at the heating rate of 1 ℃/min to obtain the sample, namely the foliated CoNi-NC micro array.
Example 3
1.314g of 2-methylimidazole, 0.465g of Co (NO) 3 ) 2 ·6H 2 O and 0.207g Fe (NO) 3 ) 3 ·9H 2 O is added into 40mL deionized water solution respectively, and dissolved by ultrasonic treatment for 5 min. And then adding the obtained mixed solution of cobalt nitrate and ferric nitrate into the 2-methylimidazole solution, and uniformly mixing. ThenThe carbon cloth was placed vertically in the mixed solution and allowed to stand at room temperature for 4 hours. And washing the obtained carbon cloth with the purple color, and then putting the carbon cloth into a 60 ℃ oven for drying for 24 hours. Spreading the dried sample in a quartz boat, placing in a tube furnace for pyrolysis, wherein the pyrolysis atmosphere is nitrogen, and pyrolyzing for 3 hours at 600 ℃ at the heating rate of 1 ℃/min to obtain the sample which is the foliated CoFe-NC micro array.
Example 4
1.314g of 2-methylimidazole, 0.465g of Co (NO) 3 ) 2 ·6H 2 O and 0.096g Cu (NO) 3 ) 3 ·6H 2 O is added into 40mL deionized water solution respectively, and dissolved by ultrasonic treatment for 5 min. And then adding the obtained mixed solution of cobalt nitrate and copper nitrate into the 2-methylimidazole solution, and uniformly mixing. The carbon cloth was then placed vertically into the mixed solution and allowed to stand at room temperature for 4 hours. And washing the obtained carbon cloth with the purple color, and then putting the carbon cloth into a 60 ℃ oven for drying for 24 hours. Spreading the dried sample in a quartz boat, placing in a tube furnace for pyrolysis, wherein the pyrolysis atmosphere is nitrogen, and pyrolyzing for 3 hours at 600 ℃ at the heating rate of 1 ℃/min to obtain the sample which is the foliated CoCu-NC micro array.
Example 5
1.314g of 2-methylimidazole, 0.586g of Co (NO 3 ) 2 ·6H 2 O is added into 40mL deionized water solution respectively, and dissolved by ultrasonic treatment for 5 min. And then adding the obtained cobalt nitrate solution into the 2-methylimidazole solution, and uniformly mixing. The nickel foam was then placed vertically into the mixed solution and allowed to stand at room temperature for 4 hours. After the obtained foam nickel with the purple color is washed clean, the foam nickel is put into an oven at 60 ℃ to be dried for 24 hours. Spreading the dried sample in a quartz boat, placing in a tube furnace for pyrolysis, wherein the pyrolysis atmosphere is nitrogen, and pyrolyzing for 3 hours at 600 ℃ at the heating rate of 1 ℃/min to obtain the sample, namely the leaf-shaped Co-NC micro-array.
Example 6
1.314g of 2-methylimidazole, 0.586g of Co (NO 3 ) 2 ·6H 2 O is added into 40mL deionized water solution respectively, and dissolved by ultrasonic treatment for 5 min. Then adding the obtained cobalt nitrate solution into 2-methylimidazole solution to mixAnd (5) uniformity. The foam iron was then placed vertically into the mixed solution and allowed to stand at room temperature for 4 hours. After the obtained foam iron with the purple color is washed clean, the foam iron is put into an oven at 60 ℃ to be dried for 24 hours. Spreading the dried sample in a quartz boat, placing in a tube furnace for pyrolysis, wherein the pyrolysis atmosphere is nitrogen, and pyrolyzing for 3 hours at 600 ℃ at the heating rate of 1 ℃/min to obtain the sample, namely the leaf-shaped Co-NC micro-array.
Example 7
1.314g of 2-methylimidazole, 0.586g of Co (NO 3 ) 2 ·6H 2 O is added into 40mL deionized water solution respectively, and dissolved by ultrasonic treatment for 5 min. And then adding the obtained cobalt nitrate solution into the 2-methylimidazole solution, and uniformly mixing. The copper foil was then placed vertically into the mixed solution and allowed to stand at room temperature for 4 hours. After the copper foil which is changed into purple in color is washed clean, the copper foil is placed in an oven at 60 ℃ to be dried for 24 hours. Spreading the dried sample in a quartz boat, placing in a tube furnace for pyrolysis, wherein the pyrolysis atmosphere is nitrogen, and pyrolyzing for 3 hours at 600 ℃ at the heating rate of 1 ℃/min to obtain the sample, namely the leaf-shaped Co-NC micro-array.
Example 8
Taking 2X 3cm 2 The carbon cloth of example 1 was clamped on a Pt electrode clamp as the working electrode, an Ag/AgCl electrode as the reference electrode, and a carbon rod as the working electrode, all placed on Ni (NO 3 ) 2 ·6H 2 O (0.218 g) and Fe (NO) 3 ) 3 ·9H 2 O (0.303 g) in deionized water (50 mL). Under a three-electrode system, the applied voltage was-0.9 v vs. sce and the electrodeposition time was 50s. After the deposition is finished, the carbon cloth is washed clean, and is put into a baking oven at 60 ℃ to be dried for 24 hours, and the obtained sample is the Co-NC@NiFe-LDH material with a three-dimensional multi-level nano sheet structure, wherein the thickness of the LDH nano sheet is about 0.8nm.
Example 9
Taking 2X 3cm 2 The carbon cloth of example 1 was clamped on a Pt electrode clamp as the working electrode, an Ag/AgCl electrode as the reference electrode, and a carbon rod as the working electrode, all placed on Ni (NO 3 ) 2 ·6H 2 O (0.218 g) and Fe (NO) 3 ) 3 ·9H 2 O(0.303g) Is added to the deionized water (50 mL). Under a three-electrode system, the applied voltage was-0.9 v vs. sce and the electrodeposition time was 100s. After the deposition is finished, the carbon cloth is washed clean, and is put into a baking oven at 60 ℃ to be dried for 24 hours, and the obtained sample is the Co-NC@NiFe-LDH material with a three-dimensional multi-level nano sheet structure, wherein the thickness of the LDH nano sheet is about 1.1nm.
Example 10
Taking 2X 3cm 2 The carbon cloth of example 1 was clamped on a Pt electrode clamp as the working electrode, an Ag/AgCl electrode as the reference electrode, and a carbon rod as the working electrode, all placed on Ni (NO 3 ) 2 ·6H 2 O (0.218 g) and Fe (NO) 3 ) 3 ·9H 2 O (0.303 g) in deionized water (50 mL). Under a three-electrode system, the applied voltage was-0.9 v vs. sce and the electrodeposition time was 150s. After the deposition is finished, the carbon cloth is washed clean, and is put into a baking oven at 60 ℃ to be dried for 24 hours, and the obtained sample is the Co-NC@NiFe-LDH material with a three-dimensional multi-level nano sheet structure, wherein the thickness of the LDH nano sheet is about 1.5nm.
Example 11
Taking 2X 3cm 2 The carbon cloth of example 1 was clamped on a Pt electrode clamp as the working electrode, an Ag/AgCl electrode as the reference electrode, and a carbon rod as the working electrode, all placed on Ni (NO 3 ) 2 ·6H 2 O (0.218 g) and Fe (NO) 3 ) 3 ·9H 2 O (0.303 g) in deionized water (50 mL). Under a three-electrode system, the applied voltage was-0.9 v vs. sce and the electrodeposition time was 200s. After the deposition is finished, the carbon cloth is washed clean, and is put into a baking oven at 60 ℃ to be dried for 24 hours, and the obtained sample is the Co-NC@NiFe-LDH material with a three-dimensional multi-level nano sheet structure, wherein the thickness of the LDH nano sheet is about 1.9nm.
Example 12
Taking 2X 3cm 2 The carbon cloth of example 1 was clamped on a Pt electrode clamp as the working electrode, an Ag/AgCl electrode as the reference electrode, and a carbon rod as the working electrode, all placed on Ni (NO 3 ) 2 ·6H 2 O (0.218 g) and Fe (NO) 3 ) 3 ·9H 2 Deionized water mixed solution of O (0.303 g) (50 mL). Under a three-electrode system, the applied voltage was-0.9 v vs. sce and the electrodeposition time was 300s. After the deposition is finished, the carbon cloth is washed clean, and is put into a baking oven at 60 ℃ to be dried for 24 hours, and the obtained sample is the Co-NC@NiFe-LDH material with a three-dimensional multi-level nano sheet structure, wherein the thickness of the LDH nano sheet is about 6.0nm.
Example 13
Taking 2X 3cm 2 The carbon cloth of example 1 was clamped on a Pt electrode clamp as the working electrode, an Ag/AgCl electrode as the reference electrode, and a carbon rod as the working electrode, all placed on Ni (NO 3 ) 2 ·6H 2 O (0.145 g) and Fe (NO) 3 ) 3 ·9H 2 O (0.404 g) in deionized water (50 mL). Under a three-electrode system, the applied voltage was-0.9 v vs. sce and the electrodeposition time was 200s. After the deposition is finished, the carbon cloth is washed clean and put into a baking oven at 60 ℃ to be dried for 24 hours, and the obtained sample is the Co-NC@NiFe with a three-dimensional multi-level nano sheet structure 2 -LDH material, LDH nanoplatelets thereon having a thickness of about 1.9nm.
Example 14
Taking 2X 3cm 2 The carbon cloth of example 1 was clamped on a Pt electrode clamp as the working electrode, an Ag/AgCl electrode as the reference electrode, and a carbon rod as the working electrode, all placed on Ni (NO 3 ) 2 ·6H 2 O (0.290 g) and Fe (NO) 3 ) 3 ·9H 2 O (0.202 g) in deionized water (50 mL). Under a three-electrode system, the applied voltage was-0.9 v vs. sce and the electrodeposition time was 200s. After the deposition is finished, the carbon cloth is washed clean and put into a baking oven at 60 ℃ to be dried for 24 hours, and the obtained sample is the Co-NC@Ni with a three-dimensional multi-level nano sheet structure 2 The thickness of the LDH nanosheets on the Fe-LDHs material is about 1.9nm.
FIG. 1 is a schematic diagram of Co-NC@Ni having a three-dimensional multi-stage nano-platelet structure prepared in this example 2 SEM (scanning electron microscope) photograph of Fe-LDHs material, ultra-thin Ni can be seen 2 The Fe-LDH nano-sheets are uniformly and vertically deposited on the vane-shaped Co-NC precursor to form a typical core-shell structure; FIG. 2 is the Co-NC@Ni 2 TEM (Transmission Electron microscope) of Fe-LDHs materialsThe photo can more clearly see Co nano particles uniformly distributed in the Co-NC and ultrathin LDH nano sheet structures on the surface of the Co nano particles, and further confirms the core-shell structure of the Co nano particles; FIG. 3 is a Co-NC surface grown Ni 2 AFM (atomic force microscope) photographs of Fe-LDH nanoplatelets, it can be seen that the thickness is about 1.9nm; FIG. 4 is a Co-NC surface grown Ni 2 EPR (electron paramagnetic resonance) spectrum of the Fe-LDH nanoplatelets, it can be seen that there is a huge signal peak at g=2.003, indicating that it 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) 2 The catalyst can reach 10mA cm under the voltage of 1.55V as shown by the scanning speed of 5mv/s, 85% compensation and 50mL of KOH (1M) aqueous solution as electrolyte -2 While the voltage of the Co-NC microarray is 1.70V. FIG. 6 is a graph of the stability performance of the sample against electrocatalytic hydrolysis reaction, showing that the catalyst was stable for more than 40 hours. The structure and catalytic performance test of the Metal-NC@LDHs prepared in the other examples are basically similar to those in the example.
Example 15
Taking 2X 3cm 2 The carbon cloth of example 1 was clamped on a Pt electrode clamp as the working electrode, an Ag/AgCl electrode as the reference electrode, and a carbon rod as the working electrode, all placed on Co (NO 3 ) 2 ·6H 2 O (0.218 g) and Fe (NO) 3 ) 3 ·9H 2 O (0.303 g) in deionized water (50 mL). Under a three-electrode system, the applied voltage was-0.9 v vs. sce and the electrodeposition time was 200s. After the deposition is finished, the carbon cloth is washed clean, and is put into a baking oven at 60 ℃ to be dried for 24 hours, and the obtained sample is the Co-NC@CoFe-LDH material with a three-dimensional multi-level nano sheet structure, wherein the thickness of the LDH nano sheet is about 1.8nm. The obtained material is applied to electrocatalytic hydrolysis, and is measured at 10mA cm -2 The voltage at the current density of (2) is 1.64V.
Example 16
Taking 2X 3cm 2 The carbon cloth of example 1 was clamped on a Pt electrode clamp as the working electrode, an Ag/AgCl electrode as the reference electrode, and a carbon rod as the working electrode, all placed on Co (NO 3 ) 2 ·6H 2 O (0.218 g) and Ni (NO) 3 ) 2 ·6H 2 O (0.218 g) in deionized water (50 mL). Under a three-electrode system, the applied voltage was-0.9 v vs. sce and the electrodeposition time was 200s. After the deposition is finished, the carbon cloth is washed clean, and is put into a baking oven at 60 ℃ to be dried for 24 hours, and the obtained sample is the Co-NC@CoNi-LDH material with a three-dimensional multi-level nano sheet structure, wherein the thickness of the LDH nano sheet is about 1.7nm. The obtained material is applied to electrocatalytic hydrolysis, and is measured at 10mA cm -2 The voltage at the current density of (2) was 1.78V.
Example 17
Taking 2X 3cm 2 The carbon cloth of example 1 was clamped on a Pt electrode clamp 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 ·6H 2 O (0.222 g) and Fe (NO) 3 ) 3 ·9H 2 O (0.303 g) in deionized water (50 mL). Under a three-electrode system, the applied voltage was-0.9 v vs. sce and the electrodeposition time was 200s. After the deposition is finished, the carbon cloth is washed clean, and is put into a baking oven at 60 ℃ to be dried for 24 hours, and the obtained sample is the Co-NC@ZnFe-LDH material with a three-dimensional multi-level nano sheet structure, wherein the thickness of the LDH nano sheet is about 1.8nm. The obtained material is applied to electrocatalytic hydrolysis, and is measured at 10mA cm -2 The voltage at the current density of (2) was 1.70V.
Example 18
Taking 2X 3cm 2 The carbon cloth of example 1 was clamped on a Pt electrode clamp as the working electrode, an Ag/AgCl electrode as the reference electrode, and a carbon rod as the working electrode, all placed on MgSO 4 ·7H 2 O (0.185 g) and Fe (NO) 3 ) 3 ·9H 2 O (0.303 g) in deionized water (50 mL). Under a three-electrode system, the applied voltage was-0.9 v vs. sce and the electrodeposition time was 200s. After the deposition is finished, the carbon cloth is washed clean, and is put into a baking oven at 60 ℃ to be dried for 24 hours, and the obtained sample is the Co-NC@MgFe-LDH material with a three-dimensional multi-level nano sheet structure, wherein the thickness of the LDH nano sheet is about 1.7nm. The obtained material is applied to electrocatalytic hydrolysis, and is measured at 10mA cm -2 The voltage at the current density of (2) is 1.74V.
Example 19
Taking 2X 3cm 2 The carbon cloth without Co-NC material is clamped on the Pt electrode clamp to be used as a working electrode, the Ag/AgCl electrode is used as a reference electrode, the carbon rod is used as the working electrode, and the carbon cloth is arranged on Ni (NO) 3 ) 2 ·6H 2 O (0.290 g) and Fe (NO) 3 ) 3 ·9H 2 O (0.202 g) in deionized water (50 mL). Under a three-electrode system, the applied voltage was-0.9 v vs. sce and the electrodeposition time was 200s. After the deposition is finished, the carbon cloth is washed clean and put into a baking oven at 60 ℃ to be dried for 24 hours, and the obtained sample is the Ni with the nano sheet structure 2 The thickness of the LDH nanosheets on the Fe-LDHs material is about 22nm.
The above-described embodiments are intended to illustrate the present invention, not to limit it, and any modifications and variations made thereto are within the spirit of the invention and the scope of the appended claims.

Claims (7)

1. The preparation method of the ultrathin hydrotalcite nanosheet coupled metal and nitrogen co-doped porous carbon array composite material is characterized by comprising the following steps of:
(1) Adding an organic ligand into deionized water to obtain an organic ligand solution; dissolving metal salt in deionized water to obtain a metal salt solution; the organic ligand is 2-methylimidazole; the metal salt is one or more of nitrate, chloride and acetate of cobalt, zinc, nickel, copper and iron;
(2) Adding the Metal salt solution obtained in the step (1) into an organic ligand solution, uniformly mixing, then placing into a conductive substrate, standing, washing and drying to obtain a Metal-ZIF-L material; the molar ratio of the organic ligand to the metal salt is (0.5-16): 1, a step of; the conductive substrate is any one of carbon cloth, carbon paper, foam nickel, foam iron, foam copper and copper foil; the conductive substrate is vertically placed into the mixed solution;
(3) Pyrolyzing the Metal-ZIF-L material in the step (2) in an inert atmosphere to obtain a Metal-NC material;
(4) Adding the Metal-NC material in the step (3) into deionized water solution of Metal salt, performing electrodeposition, washing and drying to obtain a Metal-NC@LDHs material; the metal salt is one or more of nitrate, chloride and acetate of cobalt, zinc, nickel, iron and magnesium; the concentration of the metal salt in the deionized water solution of the metal salt is 0.01-0.03 mol/L; the voltage of the electrodeposition is-15 to-0.01-V, and the electrodeposition time is 10-200 s.
2. The method according to claim 1, wherein the standing time in the step (2) is 0.1 to 48 hours.
3. The method of claim 1, wherein the inert atmosphere in step (3) is nitrogen or argon; the pyrolysis temperature is 300-1100 ℃, and the pyrolysis time is 0.1-48 h.
4. The method of claim 1, wherein the electrodeposition employs a three electrode system comprising a reference electrode, a counter electrode and a working electrode.
5. The method according to claim 4, wherein the reference electrode is Ag/AgCl, hg/Hg 2 Cl 2 And any one of Hg/HgO electrodes, wherein the counter electrode is any one of a carbon rod, a platinum sheet or a platinum wire, and the working electrode is a conductive substrate with a Metal-NC material clamped by a Pt or glassy carbon electrode clamp.
6. The ultrathin hydrotalcite nanosheet coupled metal and nitrogen co-doped porous carbon array composite material prepared by the preparation method of any one of claims 1-5, wherein the thickness of hydrotalcite nanosheets in the ultrathin hydrotalcite nanosheet coupled metal and nitrogen co-doped porous carbon array composite material is 0.5-1.9 nm.
7. The use of the ultra-thin hydrotalcite nanosheet coupled metal and nitrogen co-doped porous carbon array composite material of claim 6 in catalytic hydrogen production.
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