CN111921549A - Pod-shaped NiS2@ NC nano composite electrode material and preparation method thereof - Google Patents
Pod-shaped NiS2@ NC nano composite electrode material and preparation method thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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Abstract
The invention provides pod-shaped NiS2The @ NC nanometer composite electrode material is prepared with NaOH and NiSO as material4Synthesizing a nanowire precursor by simple hydrothermal reaction, and then preparing a nitrogen-doped carbon material by using glucose as a green carbon source and PVP as a nitrogen source through a hydrothermal method, wherein the nitrogen-doped carbon material is Ni (OH)2The precursor is carbon-coated, and finally, the NiS product is obtained through high-temperature calcination and vulcanization2@ NC. In the composite material, nickel sulfide particles are uniformly distributed in the pod-shaped nitrogen-doped carbon material, and a certain gap exists between the particles, so that the structure can prevent the aggregation and accumulation of nanoparticles in long-term electrochemical reaction, and the stability and the electrochemical performance of the structure are improved.
Description
Technical Field
The invention relates to a legume-shaped NiS2A @ NC nano composite electrode material and a preparation method thereof, belonging to the technical field of energy conversion and electrode materials.
Background
With the development of social industry, the problems of energy crisis and environmental pollution caused by the large consumption of fossil fuels are gradually highlighted, and in order to effectively deal with the problems, researchers strive to find new environment-friendly renewable energy sources. Wherein, the hydrogen can be regenerated with zero pollution (no pollution gas such as nitride and sulfide is generated by hydrogen combustion), hydrogen elements are mainly present in water, and the combustion product of the hydrogen is also water), and the efficiency is high (the combustion heat is 143kJ kg)-1About 3 times as much as gasoline, 3.9 times as much alcohol, 4.5 times as much coke) is regarded as a final energy source of the future society and is widely studied. At present, among methods for preparing hydrogen, a method for preparing hydrogen by electrolyzing water is widely researched due to easily available raw materials and environment-friendly process.
The hydrogen production method by water electrolysis has the oxygen evolution reaction on the anode and the hydrogen evolution reaction on the cathode. The problems of reaction rate reduction, electrode instability and the like caused by the introduction of an extra energy barrier due to water molecule decomposition in the water electrolysis process need to be solved. Therefore, the search for efficient and stable hydrogen evolution reaction catalyst to reduce the reaction activation energy and increase the reaction rate becomes the key point of hydrogen evolution by water electrolysis.
The hydrogen evolution catalyst is classified into a noble metal (Pt, Pb, etc.) based catalyst, a transition metal and a compound thereof. Among noble metal catalysts, Pt catalysts have good catalytic activity on hydrogen evolution from electrolyzed water, and the materials have low overpotential and high activity, but are expensive, rare in yield and easy to be poisoned, so that the popularization and the application of the materials are greatly limited. Transition metals have a large difference in activity compared to Pt-based catalysts, and in order to increase their activity, a bimetallic or polymetallic combination (e.g., Ni — Mo, Ni — Fe, etc.) may be used to generate a synergistic effect. However, in a strongly acidic or alkaline electrolyte solution, a metallic compound material suffers from corrosion and dissolution of active sites, performance degradation, and the like due to corrosion of an applied electrode potential or oxidation of oxygen. The transition metal compound is formed by doping non-metal elements in compound crystal lattices, and the introduction of the non-metal elements can improve the physical property and the chemical stability of metal, and can also greatly adjust the electronic structure of a metal carrier through structural modification accompanied by charge transfer, so that the catalytic efficiency of the high metal center is greatly improved. Common transition metal compounds that can be used as hydrogen evolution electrodes are carbides, sulfides, phosphides, nitrides and the like.
Transition Metal Sulfides (TMSs) become a class of electrolytic water hydrogen evolution catalysts with great development prospect due to the unique physicochemical properties and good conductivity of the TMSs. Among them, a series of catalysts for hydrogen evolution by electrolysis of water based on nickel sulfide are intensively studied because nickel sulfide has the advantages of rich valence state, low cost, environmental protection and the like. Such as "Nickel subsystems for electrochemical hydrogen evolution under alkaline conditions" published by Jiang et al: a case study of crystaline NiS, NiS2，and Ni3S2nanoparticles (Catal Sci Technol, 2015, 6 (4): 1077-2And Ni3S2). But the nickel-based material has poor structural stability, so that the further development of the nickel-based material is limited. In order to overcome this problem, a carbon-based material having a large specific surface area, good durability, high electrical conductivity, and structural stability may be used as a structural support, and the nickel sulfide may be composited with the carbon material, which may greatly improve the electrochemical stability of the catalyst. In recent years, nitrogen-doped carbon coating methods have attracted the interest of researchers, and nitrogen-doped carbon can enhance the electron conduction performance of materials compared with pure carbon coating. No NiS is found at present2Relevant reports of @ NC.
Disclosure of Invention
The invention aims to solve the problem of poor structural stability of nickel sulfide due to the intrinsic characteristics of the nickel sulfide.
The technical solution adopted for the purpose of the invention is that the invention is a bean pod-shaped NiS2The @ NC nano composite electrode material and the preparation method thereof comprise the following steps:
1) nanowire-like Ni (OH)2Preparing a precursor:
1.1) adding NaOH and NiSO4Placing the mixture in a high-pressure reaction kettle, adding deionized water, stirring and dissolving;
the NaOH and the NiSO4The mass ratio (g: g) is as follows: 1: 5-10;
the mass-volume ratio of NaOH to deionized water is (g: mL) to 1: 50-100;
1.2) reacting the solution obtained in the step 1.1) at 120-240 ℃ for 2-6 h;
1.3) cooling the reaction liquid in the step 1.2), centrifuging, washing, and drying at 60 ℃ to obtain a Ni (OH)2 precursor;
2) preparation of nanowire-shaped Ni @ NC intermediate:
2.1) weighing the Ni (OH) obtained in the step 1.3)2Sequentially adding deionized water, glucose solution, polyvinylpyrrolidone (PVP) and bromohexadecyltrimethylamine (CTAB) into the precursor;
the Ni (OH)2The mass-volume ratio of the precursor to the deionized water is (g: mL): 1: 200-500;
the Ni (OH)2The mass ratio (g: g) of the precursor, the glucose solution, the polyvinylpyrrolidone and the bromohexadecyl trimethylamine is as follows: 1: 5-15: 0.1-0.5;
2.2) reacting the solution obtained in the step 2.1) at 120-240 ℃ for 6-16 h;
2.3) naturally cooling the solution obtained in the step 2.2), centrifugally washing, and drying at 60 ℃;
2.4) placing the sample in the step 2.3) into a tube furnace, and continuously introducing argon and hydrogen (Ar/H)24), calcining at 400-1000 ℃ for 3-6 h to obtain a nanowire-shaped Ni @ NC intermediate;
3) legume NiS2Preparation of @ NC nanocomposite:
3.1) putting a certain amount of the Ni @ NC intermediate prepared in the step 2.4) into a glass tube, calcining for 2-4 h at 250 ℃ in a tube furnace by taking thiourea as a sulfur source, and continuously introducing argon gas in the process to finally obtain the legume NiS2@ NC nanocomposites.
Compared with the prior art, the invention has the following remarkable advantages:
(1) NiS prepared by the invention2@ NC shows higher catalytic activity and small initial overpotential;
(2) pod-shaped NiS prepared by the invention2The unique carbon coating structure of the @ NC nano composite material prevents the aggregation and the peeling of active sites, and greatly improves the structural stability and the chemical stability of the material;
(3) the introduction of the nitrogen element improves the conductivity of the composite material and further improves the electrochemical performance of the composite material.
Drawings
FIG. 1 is a diagram of legume NiS prepared in example 12SEM (a) picture and TEM (b) picture of @ NC.
FIG. 2 shows NiS prepared in examples 1 to 32@NC、NiS2@ C and NiS2At 0.5mol/L H2SO4Linear Sweep Voltammetry (LSV) curves below.
FIG. 3 NiS prepared in examples 1 to 32@NC、NiS2@ C and NiS2At a current density of 10mA/cm2Stability test of the following.
SEM (FIG. 1a) and TEM (FIG. 1b) show that NiS was prepared2The @ NC is a pod-shaped structure, the nickel nanoparticles coated by the carbon film are arranged regularly and at intervals, the structure can prevent the nanoparticles from being aggregated and accumulated in long-time electrochemical reaction, and the carbon-coated and nitrogen-doped pod-shaped NiS2The @ NC onset overpotential is very small (fig. 2), exhibiting high catalytic activity and stability (fig. 3).
Detailed Description
The present invention will be further described with reference to the following examples and drawings, but it should not be understood that the scope of the subject matter described above is limited to the following examples and drawings. Various substitutions and alterations can be made without departing from the technical idea of the invention and the scope of the invention is covered by the present invention according to the common technical knowledge and the conventional means in the field.
Example 1:
1) nanowire-like Ni (OH)2Preparing a precursor:
1.1) weigh 0.392g NaOH, 2.576g NiSO4Placing the mixture into a high-pressure reaction kettle, adding 30mL of deionized water, stirring and dissolving;
1.2) reacting the solution obtained in the step 1.1) for 3 hours at 160 ℃;
1.3) cooling the reaction liquid in the step 1.2), centrifuging, washing, and drying at 60 ℃ to obtain Ni (OH)2A precursor;
2) preparation of nanowire-shaped Ni @ NC intermediate:
2.1) 0.1g of the Ni (OH) obtained in step 1.3) are weighed2Adding 30mL of deionized water, 1g of glucose, 0.02g of polyvinylpyrrolidone and 0.02g of bromohexadecyl trimethylamine into the precursor in sequence;
2.2) reacting the solution obtained in the step 2.1) for 8 hours at 180 ℃;
2.3) naturally cooling the solution obtained in the step 2.2), centrifugally washing, and drying at 60 ℃;
2.4) placing the sample in the step 2.3) into a tube furnace, and continuously introducing argon and hydrogen (Ar/H)24), calcining for 3h at 700 ℃ to obtain a nanowire-shaped Ni @ NC intermediate;
3) legume NiS2Preparation of @ NC nanocomposite:
3.1) putting 0.2g of the Ni @ NC intermediate prepared in the step 2.4) into a glass tube, adding 0.1g of thiourea, calcining for 2 hours at 250 ℃ in a tube furnace, continuously introducing argon in the process, and finally obtaining the legume NiS2@ NC nanocomposites.
Example 2:
1) nanowire-like Ni (OH)2Preparing a precursor:
1.1) weigh 0.392g NaOH, 2.576g NiSO4Placing the mixture into a high-pressure reaction kettle, adding 30mL of deionized water, stirring and dissolving;
1.2) reacting the solution obtained in the step 1.1) at 160 ℃ for 3 h;
1.3) cooling the reaction liquid in the step 1.2), centrifuging, washing, and drying at 60 ℃ to obtain Ni (OH)2A precursor;
2) preparation of nanowire-shaped Ni @ C intermediate:
2.1) 0.1g of the Ni (OH) obtained in step 1.3) are weighed2Adding 30mL of deionized water and 1g of glucose into the precursor in sequence;
2.2) reacting the solution obtained in the step 2.1) for 8 hours at 180 ℃;
2.3) naturally cooling the solution obtained in the step 2.2), centrifugally washing, and drying at 60 ℃;
2.4) placing the sample in the step 2.3) into a tube furnace, and continuously introducing argon and hydrogen (Ar/H)24), calcining for 3h at 700 ℃ to obtain a nanowire-shaped Ni @ C intermediate;
3) legume NiS2Preparation of @ NC nanocomposite:
3.1) putting 0.2g of the Ni @ C intermediate prepared in the step 2.4) into a glass tube, adding 0.1g of thiourea, calcining for 2 hours at 250 ℃ in a tube furnace, continuously introducing argon in the process, and finally obtaining the legume NiS2@ NC nanocomposites.
Example 3:
1) nanowire-like Ni (OH)2Preparing a precursor:
1.1) weigh 0.392g NaOH, 2.576g NiSO4Placing the mixture into a high-pressure reaction kettle, adding 30mL of deionized water, stirring and dissolving;
1.2) reacting the solution obtained in the step 1.1) for 3 hours at 160 ℃;
1.3) cooling the reaction liquid in the step 1.2), centrifuging, washing, and drying at 60 ℃ to obtain Ni (OH)2A precursor;
2) preparation of nanowire-like Ni intermediate:
2.1) 0.1g of the Ni (OH) obtained in step 1.3) are weighed2Precursor body
2.4) placing the sample in the step 2.1) into a tube furnace, and continuously introducing argon and hydrogen (Ar/H)24), calcining for 3h at 700 ℃ to obtain a nanowire-shaped Ni intermediate;
3) nanowire-like NiS2Preparation of an intermediate:
3.1) 0.1g of the Ni (OH) obtained in step 1.3) are weighed2Placing the precursor in a glass tube, adding 0.1g of thiourea, calcining for 2h at 250 ℃ in a tube furnace, continuously introducing argon in the process, and finally obtaining NiS2Nanocomposite material。
Claims (3)
1. Pod-shaped NiS2The @ NC nano composite electrode material is characterized by comprising the following steps of:
1) nanowire-like Ni (OH)2Preparing a precursor:
1.1) weighing quantitative NaOH and NiSO4Placing the mixture in a high-pressure reaction kettle, adding deionized water, stirring and dissolving;
1.2) reacting the solution obtained in the step 1.1) at 120-240 ℃ for 2-6 h;
1.3) cooling the reaction liquid in the step 1.2), centrifuging, washing, and drying at 60 ℃ to obtain Ni (OH)2A precursor;
2) preparation of nanowire-shaped Ni @ NC intermediate:
2.1) weighing the Ni (OH) obtained in the step 1.3)2Sequentially adding deionized water, glucose solution, polyvinylpyrrolidone (PVP) and bromohexadecyltrimethylamine (CTAB) into the precursor;
2.2) reacting the solution obtained in the step 2.1) at 120-240 ℃ for 6-16 h;
2.3) naturally cooling the solution obtained in the step 2.2), centrifugally washing, and drying at 60 ℃;
2.4) placing the sample in the step 2.3) into a tube furnace, and continuously introducing argon and hydrogen (Ar/H)24), calcining at 400-1000 ℃ for 3-6 h to obtain a nanowire-shaped Ni @ NC intermediate;
3) legume NiS2Preparation of @ NC nanocomposite:
3.1) putting a certain amount of the Ni @ NC intermediate prepared in the step 2.4) into a glass tube, taking thiourea as a sulfur source, reacting and calcining for 2-4 h at 250 ℃ in a tube furnace, continuously introducing argon gas in the process, and finally obtaining the legume NiS2@ NC nanocomposites.
2. Pod NiS according to claim 12The @ NC nano composite electrode material and the preparation method thereof are characterized in that in the step 1.1), NaOH and NiSO are added4The mass ratio (g: g) is as follows: 1: 5-10, wherein the mass-volume ratio of NaOH to deionized water is (g: mL): 1: 50-100.
3. Pod NiS according to claim 12The @ NC nano composite electrode material and the preparation method thereof are characterized in that in the step 2.1), Ni (OH)2The mass-volume ratio of the precursor to the deionized water is (g: mL): 1: 200 to 500, said Ni (OH)2The mass ratio (g: g) of the precursor, the glucose solution, the polyvinylpyrrolidone and the bromohexadecyl trimethylamine is as follows: 1: 5-15: 0.1-0.5.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113036097A (en) * | 2021-02-04 | 2021-06-25 | 淮阴工学院 | Sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material and preparation method thereof |
| CN114984979A (en) * | 2022-06-20 | 2022-09-02 | 武汉工程大学 | High-performance NiS 2 @ C nano material and preparation method and application thereof |
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| CN115548283B (en) * | 2022-09-01 | 2024-04-19 | 河北工业大学 | NiS (nickel-zinc sulfide)2Preparation method and application of @ C/HC electrode material |
| CN115740436A (en) * | 2022-11-21 | 2023-03-07 | 重庆邮电大学 | One-dimensional core-shell structure carbon-coated ferromagnetic nanowire, and preparation method and application thereof |
| CN115740436B (en) * | 2022-11-21 | 2023-08-18 | 重庆邮电大学 | One-dimensional core-shell structure carbon-coated ferromagnetic nanowire, preparation method and application thereof |
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