CN114496582B - Hollow metal-nitrogen co-doped carbon-based nanosheet array and preparation method and application thereof - Google Patents

Hollow metal-nitrogen co-doped carbon-based nanosheet array and preparation method and application thereof Download PDF

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CN114496582B
CN114496582B CN202111516169.9A CN202111516169A CN114496582B CN 114496582 B CN114496582 B CN 114496582B CN 202111516169 A CN202111516169 A CN 202111516169A CN 114496582 B CN114496582 B CN 114496582B
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沈葵
王志桥
李映伟
陈俊英
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South China University of Technology SCUT
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Abstract

The invention discloses a hollow metal-nitrogen co-doped carbon-based nanosheet array and a preparation method and application thereof. The conductive substrate is soaked in an aqueous solution of 2-methylimidazole and zinc salt, is taken out and washed after being stood for the first time, is then soaked in an aqueous solution of 2-methylimidazole and metal salt, and is taken out and washed after being stood for the second time; repeating the operation for n times to obtain a 2 n-layer ZIF-L nanosheet array growing on the conductive substrate; drying the 2 n-layer ZIF-L nanosheet array, and pyrolyzing under the protection of inert atmosphere to obtain an n-layer hollow metal-nitrogen co-doped carbon-based nanosheet array; wherein n is an integer greater than 0. The preparation method is simple and convenient to operate, the preparation process is green and environment-friendly, the prepared product is high in purity, controllable in structure and strong in mechanical strength, the product can be directly used as an electrode material, the preparation of a large-area electrode is realized, and the prepared material and a phosphide derivative material show excellent HER performance and stability.

Description

Hollow metal-nitrogen co-doped carbon-based nanosheet array and preparation method and application thereof
Technical Field
The invention belongs to the technical field of synthesis of nano materials, and particularly relates to a hollow metal-nitrogen co-doped carbon-based nanosheet array and a preparation method and application thereof.
Background
Metal-Organic Frameworks (MOFs) are a class of Organic-inorganic hybrid materials with periodic network structure formed by self-assembling Organic ligands and Metal ions or Metal clusters. MOFs, because of their unique advantages of porous crystalline framework, ultra-high porosity and specific surface area, tunable composition and structure, exhibit great potential for applications in many fields, particularly in electrochemical energy storage and conversion, such as electrocatalysis, batteries, supercapacitors, etc. The performance of the nano material mainly depends on the components and the microstructure of the nano material, and besides the improvement of the inherent activity of a single active site, the appearance engineering exposes more active sites and strengthens the mass transfer process of the reaction, so that the nano material is another effective way for improving the performance of the material. In recent years, the MOFs-based materials with various nanostructures are widely designed, which not only helps to further improve the performance of the MOFs-based materials, but also has important significance for enriching the diversity of the nano-materials.
The multi-shell hollow material has the advantages of small mass transfer and charge transfer resistance, high specific surface area, rich and adjustable active sites, multiple boundaries and cavities and the like, generally shows excellent performance in various application fields, and is widely concerned in recent years. However, at present, it is still a great challenge to reasonably design a simple route to realize the precise and controllable synthesis of the multi-shell hollow nano material. In recent years, researchers have adopted novel MOFs materials as precursors or templates to successfully prepare a series of multi-shell hollow materials. However, most of the currently reported MOFs-based multi-shell hollow materials are powder materials, such as: multi-shell ZIF-8 (Liu X, zhang F, goh T, et al., angew. Chem., int. Ed.2018,57, 2110-2114.), ZIF-derived multi-shell Co @ NC (Chen H, shen K, tan Y, et al., ACS Nano,2019,13, 7800-7810), ZIF-67-derived multi-shell Co @ 3 O 4 (Wang L, wan J, ZHao Y, et al, J.Am. Chem.Soc.2019,141, 2238-2241) and the like, which are used in the field of electrochemical energy storage and conversion, usually require the addition of a polymer binder to coat on a conductive substrate, not only is the problem of complicated electrode preparation process, but also causes many adverse effects on the performance of the catalyst, such as increased internal resistance of the catalyst, deactivation of active centers, blockage of mass transfer channels and the like. Studies have shown that growing the catalyst in situ on a conductive substrate as a self-supporting electrode solves the above problems very well. At present, many researches report that MOFs base materials grow on a conductive substrate, but most prepared materials are solid, have small specific surface area and unsatisfactory catalytic performance, and are suitable for preparationThe preparation of the multi-shell hollow nano array material grown on the conductive substrate for further improving the HER catalytic performance has not been reported.
Disclosure of Invention
The invention provides a preparation method of a multilayer hollow metal-nitrogen co-doped carbon-based nanosheet array supported by a conductive substrate, aiming at the problems of complex working procedures and performance attenuation in the process of preparing an electrode by using a traditional multi-shell powder material. The method is simple and convenient to operate, the preparation process is green and environment-friendly, the prepared product is high in purity, controllable in structure and strong in mechanical strength, and can be directly used as an electrode material and can realize the preparation of large-area electrodes.
The invention is realized by the following technical scheme.
A preparation method of a hollow metal-nitrogen co-doped carbon-based nanosheet array comprises the following steps:
soaking a conductive substrate in an aqueous solution of 2-methylimidazole and zinc salt, standing for the first time, taking out and washing, then soaking in an aqueous solution of 2-methylimidazole and metal salt, standing for the second time, taking out and washing;
repeating the operation for n times to obtain a 2 n-layer ZIF-L nanosheet array growing on the conductive substrate;
drying the 2 n-layer ZIF-L nanosheet array, and pyrolyzing under the protection of inert atmosphere to obtain an n-layer hollow metal-nitrogen co-doped carbon-based nanosheet array;
wherein n is an integer greater than 0.
Preferably, the conductive substrate is one of carbon cloth, carbon fiber, foamed nickel, foamed aluminum, foamed copper and foamed cobalt.
Preferably, the zinc salt is one or more of nitrate, chloride and acetate of zinc; the metal salt is one or more of nitrates, chlorides and acetates of cobalt, zinc, nickel, copper and iron.
Preferably, the molar concentration of the 2-methylimidazole in the aqueous solution of the 2-methylimidazole and the zinc salt is 0.04-6 mol/L, and the molar concentration of the zinc salt is 0.01-4 mol/L; the molar concentration of the 2-methylimidazole in the aqueous solution of the 2-methylimidazole and the metal salt is 0.04-6 mol/L, and the molar concentration of the metal salt is 0.01-4 mol/L.
Preferably, the first standing time is 0.2-48 h; the second standing time is 0.2-48 h.
Preferably, the conductive substrate is vertically immersed in an aqueous solution of 2-methylimidazole and a metal salt.
Preferably, the washing is rinsing with deionized water.
Preferably, the inert atmosphere is nitrogen or argon;
preferably, the pyrolysis temperature is 300-1100 ℃, and the pyrolysis time is 0.1-24 h.
Preferably, n is an integer of 1 to 7. More preferably, n is an integer of 1 to 5.
The hollow metal-nitrogen co-doped carbon-based nanosheet array prepared by the preparation method.
Preferably, the thickness of the nanosheet of the hollow metal-nitrogen co-doped carbon-based nanosheet array is 50-500 nm, the width of the nanosheet is 0.2-10 microns, the number of layers of the hollow structure is 1-7, the metal content is 2-70 wt%, the nitrogen content is 1-20 wt%, and the carbon content is 10-95 wt%. More preferably, the number of layers of the hollow structure is 1 to 5.
The hollow metal-nitrogen co-doped carbon-based nanosheet array is applied to electrolytic hydrogen production or preparation of hydrogen evolution electrodes.
Preferably, the hollow metal-nitrogen co-doped carbon-based nanosheet array is subjected to phosphating treatment.
Further preferably, the phosphating treatment specifically comprises: under the protection of inert atmosphere, the hollow metal-nitrogen co-doped carbon-based nanosheet array and the phosphorus source are treated at the temperature of 300-400 ℃ for 1-3 h.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the multilayer hollow metal-nitrogen co-doped carbon-based nanosheet array growing on the conductive substrate is prepared for the first time, and the number of shell layers can be regulated and controlled according to the number of growing layers of ZIFs precursors. The method has the advantages of simple operation, green and environment-friendly preparation process, high purity of the prepared product, controllable structure, strong mechanical strength, direct use as electrode material, and realization of large-area electrode (20 × 20 cm) 2 ) The prepared material and the phosphide-derived material show excellent HER performance and stability.
Drawings
FIG. 1 is a scanning electron microscope and a transmission electron microscope image of a single-layer hollow Co @ NC nanosheet array prepared in example 1 of the present invention.
FIG. 2 is a scanning electron microscope and a transmission electron microscope image of a double-layer hollow Co @ NC nanosheet array prepared in example 2 of the present invention.
FIG. 3 is a scanning electron microscope and a transmission electron microscope image of a three-layer hollow Co @ NC nanosheet array prepared in example 3 of the present invention.
FIG. 4 is an X-ray diffraction pattern of the single-layer hollow prepared in example 1, the double-layer hollow prepared in example 2, and the three-layer hollow Co @ NC nanosheet array prepared in example 3, in accordance with the present invention.
FIG. 5 shows that the single-layer prepared in example 1 and the three-layer hollow Co @ NC nanosheet array prepared in example 3 are 0.5M H 2 SO 4 And the stability performance of the three-layer hollow co @ nc nanosheet array prepared in example 3.
FIG. 6 shows that the array of solid, single-layer hollow prepared in example 8, double-layer hollow prepared in example 9, and three-layer hollow Co/CoP @ NC nanosheets prepared in example 10 is 0.5M H, according to the present invention 2 SO 4 HER performance profile of (a).
FIG. 7 is a graph of the stability of a three-layer hollow Co/CoP @ NC nanosheet array prepared in example 10 of the present invention.
Detailed Description
Specific embodiments of the present invention will be further described below with reference to the drawings and examples, but the present invention is not limited thereto.
Example 1
(1) Preparation of two-layer ZIF-L nanosheet array
Zinc nitrate (0.51 g), cobalt nitrate (0.58 g), 2-methylimidazole (1.116 g) and 2-methylimidazole (1.314 g) were dissolved in 40ml of deionized water respectively and dispersed by ultrasound to obtain clear solutions A, B, C and D. Subsequently, the solution A was added to the solution C and stirred uniformly for a certain period of time (1-2 min), and then the area was 3.5X 2.5cm 2 Vertically soaking the pretreated carbon cloth in the mixed solution A and C, standing for 3h, taking out, washing with deionized water for multiple times, vertically soaking in the mixed solution B and D again, standing for 1h, taking out, washing with deionized water for multiple times, and vacuum drying at 65 ℃ for 12h to obtain a two-layer ZIF-L nanosheet array (2L-ZIF-L/CC for short) growing on the carbon cloth.
(2) Preparation of single-layer hollow cobalt-nitrogen co-doped carbon-based nanosheet array
Transferring the 2L-ZIF-L/CC into a tubular furnace, heating the mixture to 650 ℃ from room temperature at the speed of 1 ℃/min under the protection of argon atmosphere, carrying out pyrolysis for 3h, then naturally cooling the mixture to room temperature, and taking out a sample to obtain a single-layer hollow cobalt-nitrogen co-doped carbon-based nanosheet array (1 LH-Co @ NC/CC for short).
Fig. 1 is a scanning electron microscope image and a transmission electron microscope image of the present embodiment, which clearly shows that the nanosheets uniformly grow on the carbon fiber, and the nanosheets are in a single-layer hollow structure. As shown in FIG. 4, the main phase is metallic Co through X-ray diffraction identification.
Example 2
(1) Preparation of four-layer ZIF-L nanosheet array
Zinc nitrate (0.51 g), cobalt nitrate (0.58 g), 2-methylimidazole (1.116 g) and 2-methylimidazole (1.314 g) were dissolved in 40ml of deionized water respectively and dispersed by ultrasound to obtain clear solutions A, B, C and D. And then vertically soaking the 2L-ZIF-L/CC in the embodiment 1 in the mixed solution of A and C, standing for 1h, taking out, washing with deionized water for multiple times, vertically soaking in the mixed solution of B and D again, standing for 1h, taking out, washing with deionized water for multiple times, and vacuum drying at 65 ℃ for 12h to obtain the four-layer ZIF-L nanosheet array (4L-ZIF-L/CC for short) growing on the carbon cloth.
(2) Preparation of double-layer hollow cobalt-nitrogen co-doped carbon-based nanosheet array
Transferring 4L-ZIF-L/CC into a tubular furnace, heating from room temperature to 650 ℃ at the speed of 1 ℃/min under the protection of argon atmosphere, pyrolyzing for 3h, naturally cooling to room temperature, and taking out a sample to obtain the double-layer hollow cobalt-nitrogen co-doped carbon-based nanosheet array (2 LH-Co @ NC/CC for short).
Fig. 2 is a scanning electron microscope image and a transmission electron microscope image of the present embodiment, it can be clearly seen that the nanosheets uniformly grow on the carbon fiber, and the nanosheets are of a double-layer hollow structure. As shown in FIG. 4, the main phase is metallic Co through X-ray diffraction identification.
Example 3
(1) Preparation of six-layer ZIF-L nanosheet array
Zinc nitrate (0.51 g), cobalt nitrate (0.58 g), 2-methylimidazole (1.116 g) and 2-methylimidazole (1.314 g) were dissolved in 40ml of deionized water respectively and dispersed by ultrasound to give clear solutions A, B, C and D. And then vertically soaking 4L-ZIF-L/CC in the mixed solution of A and C in the embodiment 2, standing for 1h, taking out, washing with deionized water for multiple times, vertically soaking in the mixed solution of B and D again, standing for 1h, taking out, washing with deionized water for multiple times, and vacuum drying at 65 ℃ for 12h to obtain a six-layer ZIF-L nanosheet array (6L-ZIF-L/CC for short) growing on the carbon cloth.
(2) Preparation of three-layer hollow cobalt-nitrogen co-doped carbon-based nanosheet array
Transferring 6L-ZIF-L/CC into a tubular furnace, heating from room temperature to 650 ℃ at the speed of 1 ℃/min under the protection of argon atmosphere, pyrolyzing for 3h, naturally cooling to room temperature, and taking out a sample to obtain a three-layer hollow cobalt-nitrogen co-doped carbon-based nanosheet array (3 LH-Co @ NC/CC for short).
Fig. 3 is a scanning electron microscope image and a transmission electron microscope image of the present embodiment, and it can be clearly seen that the nanosheets uniformly grow on the carbon fiber, and the nanosheets are in a three-layer hollow structure. As shown in FIG. 4, the main phase is metallic Co through X-ray diffraction identification.
FIG. 5 is a graph showing HER performance in this example and example 1, and it can be seen that 3LH-Co @ NC/CC hasExcellent HER performance at 10mA cm -2 The overpotential of the three-layer hollow structure is only 110mV under the current density, which is obviously superior to that of the 1LH-Co @ NC/CC material, and the three-layer hollow structure has better performance on electrocatalysis. And 3LH-Co @ NC/CC at 10mA cm -2 The current density of the high-voltage power supply can stably work for 10 hours, and the overpotential is not obviously increased, so that the high-voltage power supply is proved to have excellent constant-current stability.
Example 4
(1) Preparation of eight-layer ZIF-L nanosheet array
Zinc nitrate (0.51 g), cobalt nitrate (0.58 g), 2-methylimidazole (1.116 g) and 2-methylimidazole (1.314 g) were dissolved in 40ml of deionized water respectively and dispersed by ultrasound to obtain clear solutions A, B, C and D. And then, vertically soaking the 6L-ZIF-L/CC in the mixed solution of A and C in the embodiment 3, standing for 1h, taking out, washing with deionized water for multiple times, vertically soaking in the mixed solution of B and D again, standing for 1h, taking out, washing with deionized water for multiple times, and vacuum drying at 65 ℃ for 12h to obtain the eight-layer ZIF-L nanosheet array (8L-ZIF-L/CC for short) growing on the carbon cloth.
(2) Preparation of four-layer hollow cobalt-nitrogen co-doped carbon-based nanosheet array
Transferring 8L-ZIF-L/CC into a tubular furnace, heating from room temperature to 650 ℃ at the speed of 1 ℃/min under the protection of argon atmosphere, pyrolyzing for 3h, naturally cooling to room temperature, and taking out a sample to obtain a four-layer hollow cobalt-nitrogen co-doped carbon-based nanosheet array (4 LH-Co @ NC/CC for short).
Example 5
(1) Preparation of ten-layer ZIF-L nanosheet array
Zinc nitrate (0.51 g), cobalt nitrate (0.58 g), 2-methylimidazole (1.116 g) and 2-methylimidazole (1.314 g) were dissolved in 40ml of deionized water respectively and dispersed by ultrasound to obtain clear solutions A, B, C and D. And then, vertically soaking 8L-ZIF-L/CC in the mixed solution of A and C in the embodiment 4, standing for 1h, taking out, washing with deionized water for multiple times, vertically soaking in the mixed solution of B and D again, standing for 1h, taking out, washing with deionized water for multiple times, and vacuum drying at 65 ℃ for 12h to obtain ten layers of ZIF-L nanosheet arrays (10L-ZIF-L/CC for short) growing on the carbon cloth.
(2) Preparation of five-layer hollow cobalt-nitrogen co-doped carbon-based nanosheet array
Transferring 10L-ZIF-L/CC into a tubular furnace, heating from room temperature to 650 ℃ at the speed of 1 ℃/min under the protection of argon atmosphere, pyrolyzing for 3h, naturally cooling to room temperature, and taking out a sample to obtain a five-layer hollow cobalt-nitrogen co-doped carbon-based nanosheet array (5 LH-Co @ NC/CC for short).
Example 6
(1) Preparation of Single-layer ZIF-L nanosheet array
Metal salts (zinc nitrate: 0.291g and cobalt nitrate: 0.297 g) and 2-methylimidazole (1.314 g) were dissolved in 40ml of deionized water respectively and dispersed by ultrasound to give clear solutions a, b. Subsequently, the solution a was added to the solution b and stirred uniformly for a certain period of time (1-2 min), and then the area was set to 3.5X 2.5cm 2 Vertically soaking the pretreated carbon cloth in the mixed solution a and b, standing for 3h, taking out, washing with deionized water for multiple times, and vacuum-drying at 65 ℃ for 12h to obtain a single-layer ZIF-L nanosheet array (1L-ZIF-L/CC for short) growing on the carbon cloth.
(2) Preparation of solid cobalt-nitrogen co-doped carbon-based nanosheet array
Transferring 1L-ZIF-L/CC into a tube furnace, heating from room temperature to 650 ℃ at the speed of 1 ℃/min under the protection of argon atmosphere, pyrolyzing for 3h, naturally cooling to room temperature, and taking out a sample to obtain a solid cobalt-nitrogen co-doped carbon-based nanosheet array (S-Co @ NC/CC for short).
Example 7
Transferring the S-Co @ NC/CC obtained in the example 6 into a tube furnace, placing 1g of sodium hypophosphite at the upstream position of the tube, heating the tube to 350 ℃ from room temperature at the heating rate of 2 ℃/min under the protection of argon atmosphere, keeping the tube for 2h, then naturally cooling the tube to room temperature, and taking out a sample to obtain the Co/CoP nanoparticle-loaded solid nitrogen-doped carbon nanosheet array (S-Co/CoP @ NC/CC).
Example 8
Transferring the 1LH-Co @ NC/CC obtained in the example 1 into a tube furnace, placing 1g of sodium hydrogen phosphate at the upstream position of the tube, heating the tube to 350 ℃ from room temperature at the heating rate of 2 ℃/min under the protection of argon atmosphere, keeping the tube for 2h, then naturally cooling the tube to room temperature, and taking out a sample to obtain the single-layer hollow nitrogen-doped carbon nanosheet array (1 LH-Co/CoP @ NC/CC) loaded with the Co/CoP nanoparticles.
Example 9
Transferring the 2LH-Co @ NC/CC obtained in the example 2 into a tube furnace, placing 1g of sodium hydrogen phosphate at the upstream position of the tube, heating the tube to 350 ℃ from room temperature at the heating rate of 2 ℃/min under the protection of argon atmosphere, keeping the tube for 2h, then naturally cooling the tube to room temperature, and taking out a sample to obtain the Co/CoP nanoparticle-loaded double-layer hollow nitrogen-doped carbon nanosheet array (2 LH-Co/CoP @ NC/CC).
Example 10
Transferring the 3LH-Co @ NC/CC obtained in the embodiment 3 into a tube furnace, placing 1g of sodium hydrogen phosphate at the upstream position of the tube, heating the tube to 350 ℃ from room temperature at the heating rate of 2 ℃/min under the protection of argon atmosphere, keeping the tube for 2h, then naturally cooling the tube to room temperature, and taking out a sample to obtain the Co/CoP nanoparticle-loaded three-layer hollow nitrogen-doped carbon nanosheet array (3 LH-Co/CoP @ NCCC).
FIG. 6 shows the results of this example and examples 7, 8 and 9 at 0.5 MH 2 SO 4 The HER performance graph of (1) shows that 3LH-Co/CoP @ NC/CC has the optimal HER performance at 10mA cm -2 And 50mA cm -2 The overpotential under the current density of the material is respectively 86mV and 153mV, which is obviously lower than that of a solid material (200 mV and 273 mV), a single-layer hollow material (142 mV and 226 mV) and a double-layer hollow material (112 mV and 186 mV), and the three-layer hollow structure Co/CoP @ NC/CC material has better HER performance.
FIG. 7 shows the present embodiment at 0.5 MH 2 SO 4 The HER stability graph of (3 LH-Co @ NC/CC at 10mA cm) -2 The current density of the electrode can stably work for 16 hours, and the overpotential is not obviously increased, thereby proving that the electrode has excellent constant current stability.
Example 11
0.51g of zinc nitrate, a total of 2mmol of metal salt (cobalt nitrate: 0.465g, ferric nitrate: 0.096 g), 1.116g of 2-methylimidazole and 1.314g of 2-methylimidazole were dissolved in 40ml of deionized water respectively and ultrasonically dispersed to obtain clear solutions A, E, C and D. Then, the solution A is added into the solution C and is uniformly stirred to a certain degreeFor a period of time (1-2 min), and then the area was 3.5X 2.5cm 2 Vertically soaking the pretreated carbon cloth in the mixed solution of the A and the C, standing for 3 hours, taking out the carbon cloth, washing the carbon cloth with deionized water for multiple times, vertically soaking the carbon cloth in the mixed solution of the E and the D again, standing for 1 hour, taking out the carbon cloth, and washing the carbon cloth with deionized water for multiple times. And then soaking the substrate in the mixed solution of the A and the C again, standing for 1h, taking out, washing with deionized water for multiple times, then soaking in the mixed solution of the E and the D, standing for 1h, taking out, washing with deionized water for multiple times, repeating the process once again, performing vacuum drying at 65 ℃ for 12h, placing in a tubular furnace, heating from room temperature to 650 ℃ at the speed of 1 ℃/min under the protection of argon atmosphere, performing pyrolysis for 3h, naturally cooling to room temperature, and taking out a sample to obtain the three-layer hollow nitrogen-doped carbon-based nanosheet array (3 LH-CoCu @ NC/CC for short) loaded with the CoCu alloy nanoparticles.
Example 12
0.51g of zinc nitrate, a total of 2mmol of metal salt (cobalt nitrate: 0.465g, ferric nitrate: 0.16 g), 1.116g of 2-methylimidazole and 1.314g of 2-methylimidazole were dissolved in 40ml of deionized water respectively and dispersed by ultrasound to obtain clear solutions A, F, C and D. Subsequently, the solution A was added to the solution C and stirred uniformly for a certain period of time (1-2 min), and then the area was 3.5X 2.5cm 2 Vertically soaking the pretreated carbon cloth in the mixed solution of the A and the C, standing for 3 hours, taking out the carbon cloth, washing the carbon cloth with deionized water for multiple times, vertically soaking the carbon cloth in the mixed solution of the F and the D again, standing for 1 hour, taking out the carbon cloth, and washing the carbon cloth with deionized water for multiple times. And then soaking the mixture in the mixed solution A and C again, standing for 1h, taking out, washing with deionized water for multiple times, then soaking in the mixed solution F and D, standing for 1h, taking out, washing with deionized water for multiple times, repeating the process once again, then vacuum-drying at 65 ℃ for 12h, placing in a tubular furnace, heating from room temperature to 650 ℃ at the rate of 1 ℃/min under the protection of argon atmosphere, pyrolyzing for 3h, then naturally cooling to room temperature, and taking out a sample to obtain the three-layer hollow nitrogen-doped carbon-based nanosheet array (referred to as 3LH-CoFe @ NC/CC) loaded with the CoFe alloy nanoparticles.
Example 13
0.51g of zinc nitrate, a total of 2mmol of metal salt (cobalt nitrate: 0.465g, nitre) were addedAcid nickel: 0.12G), 1.116G of 2-methylimidazole and 1.314G of 2-methylimidazole are dissolved in 40ml of deionized water respectively and dispersed by ultrasonic to obtain clear solutions A, G, C and D. Subsequently, solution A was added to solution C and stirred uniformly for a certain period of time (1-2 min), and then the area was 3.5X 2.5cm 2 Vertically soaking the pretreated carbon cloth in the mixed solution of A and C, standing for 3h, taking out, washing with deionized water for multiple times, vertically soaking in the mixed solution of G and D again, standing for 1h, taking out, and washing with deionized water for multiple times. And then soaking the nano-particles in the mixed solution of the A and the C again, standing for 1h, taking out, washing with deionized water for multiple times, soaking in the mixed solution of the G and the D, standing for 1h, taking out, washing with deionized water for multiple times, repeating the process once again, drying in vacuum at 65 ℃ for 12h, placing in a tubular furnace, heating from room temperature to 650 ℃ at the speed of 1 ℃/min under the protection of argon atmosphere, pyrolyzing for 3h, naturally cooling to room temperature, and taking out a sample to obtain the three-layer hollow nitrogen-doped carbon-based nanosheet array (3 LH-CoNi @ NC/CC for short) loaded with the CoNi alloy nano-particles.
Example 14
Respectively dissolving 7.65g of zinc nitrate, 8.7g of cobalt nitrate, 16.74g of 2-methylimidazole and 19.71g of 2-methylimidazole in 600ml of deionized water, and performing ultrasonic dispersion to obtain clear solutions a, b, c and d. Subsequently, the solution a was added to the solution c and stirred uniformly for a certain time (1-2 min), and then the area was 20X 20cm 2 And (3) vertically soaking the pretreated carbon cloth in the mixed solution a and c, standing for 3 hours, taking out the carbon cloth, washing the carbon cloth with deionized water for multiple times, vertically soaking the carbon cloth in the mixed solution b and d again, standing for 1 hour, taking out the carbon cloth, and washing the carbon cloth with deionized water for multiple times. Then soaking in the mixed solution of a and c again, standing for 1h, taking out, washing with deionized water for multiple times, soaking in the mixed solution of b and d, standing for 1h, taking out, washing with deionized water for multiple times, repeating the process once again, and drying in vacuum at 65 ℃ for 12h. Then placing the mixture in a tube furnace, heating the mixture from room temperature to 650 ℃ at the speed of 1 ℃/min under the protection of argon atmosphere, carrying out pyrolysis for 3h, then naturally cooling the mixture to room temperature, and taking out a sample to obtain a large area (20 multiplied by 20 cm) 2 ) Three-layer hollow cobalt-nitrogen co-doped carbon-based nanosheet array supported by carbon cloth。
Example 15
0.51g of zinc nitrate, 0.58g of cobalt nitrate, 1.116g of 2-methylimidazole and 1.314g of 2-methylimidazole are respectively dissolved in 40ml of deionized water and ultrasonically dispersed to obtain clear solutions A, B, C and D. Subsequently, solution A was added to solution C and stirred uniformly for a certain period of time (1-2 min), and then the area was 3.5X 2.5cm 2 Vertically soaking the pretreated foamed nickel in the mixed solution A and C, standing for 3 hours, taking out the foamed nickel, washing the foamed nickel with deionized water for multiple times, vertically soaking the foamed nickel in the mixed solution B and D again, standing for 1 hour, taking out the foamed nickel, and washing the foamed nickel with deionized water for multiple times. And then soaking the carbon nano sheet in the mixed solution of the A and the C again, standing for 1h, taking out, washing with deionized water for multiple times, soaking in the mixed solution of the B and the D, standing for 1h, taking out, washing with deionized water for multiple times, repeating the process once again, drying in vacuum at 65 ℃ for 12h, placing in a tubular furnace, heating from room temperature to 650 ℃ at the speed of 1 ℃/min under the protection of argon atmosphere, pyrolyzing for 3h, naturally cooling to room temperature, and taking out a sample to obtain a three-layer hollow cobalt-nitrogen co-doped carbon-based nano sheet array (3 LH-Co @ NC/NF for short) growing on foamed nickel.
Example 16
Respectively dissolving 0.51g of zinc nitrate, 0.58g of cobalt nitrate, 1.116g of 2-methylimidazole and 1.314g of 2-methylimidazole in 40ml of deionized water, and performing ultrasonic dispersion to obtain clear solutions A, B, C and D. Subsequently, solution A was added to solution C and stirred uniformly for a certain period of time (1-2 min), and then the area was 3.5X 2.5cm 2 Vertically soaking the pretreated foamy copper in the mixed solution A and C, standing for 3h, taking out, washing with deionized water for multiple times, vertically soaking in the mixed solution B and D again, standing for 1h, taking out, and washing with deionized water for multiple times. Then soaking the sample in the mixed solution of the A and the C again, standing for 1h, taking out the sample, washing the sample for multiple times by using deionized water, then soaking the sample in the mixed solution of the B and the D, standing for 1h, taking out the sample, washing the sample by using the deionized water for multiple times, repeating the process once again, drying the sample in vacuum at 65 ℃ for 12h, placing the dried sample in a tubular furnace, heating the sample from room temperature to 650 ℃ at the speed of 1 ℃/min under the protection of argon atmosphere, pyrolyzing the sample for 3h, naturally cooling the sample to the room temperature, and taking out the sampleAnd obtaining the three-layer hollow cobalt-nitrogen co-doped carbon-based nanosheet array (3 LH-Co @ NC/CF for short) growing on the foamy copper.
Example 17
0.51g of zinc nitrate, 0.58g of cobalt nitrate, 1.116g of 2-methylimidazole and 1.314g of 2-methylimidazole are respectively dissolved in 40ml of deionized water and ultrasonically dispersed to obtain clear solutions A, B, C and D. Subsequently, solution A was added to solution C and stirred uniformly for a certain period of time (1-2 min), and then the area was 3.5X 2.5cm 2 Vertically soaking the pretreated foamed cobalt in the mixed solution A and C, standing for 3 hours, taking out the foamed cobalt, washing the foamed cobalt for multiple times by using deionized water, vertically soaking the foamed cobalt in the mixed solution B and D again, standing for 1 hour, taking out the foamed cobalt, and washing the foamed cobalt for multiple times by using the deionized water. And then soaking the carbon nano sheet in the mixed solution of the A and the C again, standing for 1h, taking out, washing with deionized water for multiple times, soaking in the mixed solution of the B and the D, standing for 1h, taking out, washing with deionized water for multiple times, repeating the process once again, drying in vacuum at 65 ℃ for 12h, placing in a tubular furnace, heating from room temperature to 650 ℃ at the speed of 1 ℃/min under the protection of argon atmosphere, pyrolyzing for 3h, naturally cooling to room temperature, and taking out a sample to obtain a three-layer hollow cobalt-nitrogen co-doped carbon-based nano sheet array (3 LH-Co @ NC/CBF for short) growing on foamed cobalt.
Example 18
0.51g of zinc nitrate, 0.58g of cobalt nitrate, 1.116g of 2-methylimidazole and 1.314g of 2-methylimidazole are respectively dissolved in 40ml of deionized water and ultrasonically dispersed to obtain clear solutions A, B, C and D. Subsequently, the solution A was added to the solution C and stirred uniformly for a certain period of time (1-2 min), and then the area was 3.5X 2.5cm 2 Vertically soaking the pretreated foamed aluminum in the mixed solution A and C, standing for 3 hours, taking out, washing with deionized water for multiple times, vertically soaking in the mixed solution B and D again, standing for 1 hour, taking out, and washing with deionized water for multiple times. Then soaking in the mixed solution A and C again, standing for 1h, taking out, washing with deionized water for multiple times, soaking in the mixed solution B and D, standing for 1h, taking out, washing with deionized water for multiple times, repeating the process once again, vacuum drying at 65 deg.C for 12h, placing in a tube furnace, and protecting in argon atmosphereAnd then, heating the mixture from room temperature to 650 ℃ at the speed of 1 ℃/min, carrying out pyrolysis for 3h, then naturally cooling the mixture to room temperature, and taking out a sample to obtain the three-layer hollow cobalt-nitrogen co-doped carbon-based nanosheet array (3 LH-Co @ NC/AF for short) growing on the foamed aluminum.
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 hollow metal-nitrogen co-doped carbon-based nanosheet array is characterized by comprising the following steps:
soaking a conductive substrate in an aqueous solution of 2-methylimidazole and zinc salt, standing for the first time, taking out and washing, then soaking in an aqueous solution of 2-methylimidazole and metal salt, standing for the second time, taking out and washing;
repeating the operation for n times to obtain a 2 n-layer ZIF-L nanosheet array growing on the conductive substrate;
drying the 2 n-layer ZIF-L nanosheet array, and pyrolyzing under the protection of inert atmosphere to obtain an n-layer hollow metal-nitrogen co-doped carbon-based nanosheet array;
wherein n is an integer greater than 0.
2. The method according to claim 1, wherein the conductive substrate is one of carbon cloth, carbon fiber, foamed nickel, foamed aluminum, foamed copper and foamed cobalt.
3. The preparation method of claim 1, wherein the zinc salt is one or more of nitrate, chloride and acetate of zinc; the metal salt is one or more of nitrates, chlorides and acetates of cobalt, zinc, nickel, copper and iron.
4. The preparation method according to claim 1, wherein the molar concentration of 2-methylimidazole in the aqueous solution of 2-methylimidazole and zinc salt is 0.04 to 6mol/L, and the molar concentration of zinc salt is 0.01 to 4mol/L; the molar concentration of the 2-methylimidazole in the aqueous solution of the 2-methylimidazole and the metal salt is 0.04-6 mol/L, and the molar concentration of the metal salt is 0.01-4 mol/L.
5. The preparation method of claim 1, wherein the first standing time is 0.2 to 48 hours; the second standing time is 0.2-48 h; the conductive substrate is vertically immersed in an aqueous solution of 2-methylimidazole and a metal salt; the washing is washing with deionized water.
6. The method according to claim 1, wherein the inert atmosphere is nitrogen or argon; the pyrolysis temperature is 300-1100 ℃, and the pyrolysis time is 0.1-24 h; and n is an integer of 1-7.
7. The hollow metal-nitrogen co-doped carbon-based nanosheet array prepared by the preparation method of any one of claims 1-6.
8. The hollow metal-nitrogen co-doped carbon-based nanosheet array according to claim 7, wherein the nanosheet of the hollow metal-nitrogen co-doped carbon-based nanosheet array has a thickness of 50-500 nm and a width of 0.2-10 μm, the number of layers of the hollow structure is 1-7, the metal content is 2-70 wt%, the nitrogen content is 1-20 wt%, and the carbon content is 10-95 wt%.
9. The hollow metal-nitrogen co-doped carbon-based nanosheet array of claim 7, for use in electrolytic hydrogen production or hydrogen evolution electrode preparation.
10. The use of claim 9, wherein the array of hollow metal-nitrogen co-doped carbon-based nanoplatelets is phosphated.
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