CN108615904B - Nickel cobaltate hollow sphere/carbon nitride quantum dot composite material and preparation method and application thereof - Google Patents

Nickel cobaltate hollow sphere/carbon nitride quantum dot composite material and preparation method and application thereof Download PDF

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CN108615904B
CN108615904B CN201810333614.XA CN201810333614A CN108615904B CN 108615904 B CN108615904 B CN 108615904B CN 201810333614 A CN201810333614 A CN 201810333614A CN 108615904 B CN108615904 B CN 108615904B
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hollow sphere
nickel
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李泽胜
杨蓉蓉
何伟培
孙倩倩
李泊林
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Guangdong University of Petrochemical Technology
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    • H—ELECTRICITY
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The invention relates to a nickel cobaltate hollow sphere/carbon nitride quantum dot composite material and a preparation method and application thereof. The composite material is prepared from nickel cobaltate NiCo with the molar mass ratio of 1mmol: 0.4-1.2 g2O4Hollow spheres and nitrogen carbide g-C3N4Quantum dots of said g-C3N4Quantum dots deposited on the NiCo2O4On the hollow ball. In the composite material provided by the invention, the carbon nitride quantum dots are of small-sized nano structures, so that the material utilization rate is high; the nickel cobaltate hollow spheres have the function of storing electrolyte; the nickel cobaltate hollow spheres and the carbon nitride quantum dots form a surface-dot structure distribution, have high electron/ion conductivity and excellent electrochemical catalytic performance, and can be widely applied to the field of electrochemical catalysis.

Description

Nickel cobaltate hollow sphere/carbon nitride quantum dot composite material and preparation method and application thereof
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to a nickel cobaltate hollow sphere/carbon nitride quantum dot composite material as well as a preparation method and application thereof.
Background
Currently, nickel cobaltate (NiCo)2O4) Proved to be a novel high-efficiency electro-catalytic material which can be applied to hydrogen production by water electrolysis, oxygen reduction and methanol oxidation. NiCo2O4Is Ni atom substituted for Co3O4A composite bimetal oxide obtained by mixing Co atom with main Co3O4The same spinel structure, due to the fact that the spinel structure has purer Co3O4And NiO has conductivity which is two orders of magnitude higher, so that the composite material has better electronic conductivity and higher electrochemical activity. NiCo, in particular prepared by various controlled techniques2O4The nano structure shows higher catalytic activity, lower overpotential and higher stability. Wherein NiCo is2O4The hollow sphere nano structure has larger specific surface area, abundant active sites, higher ion internal transport efficiency and good geometric structure stability, thereby being paid much attention to in the electrochemical field.
Graphite phase carbon nitride (g-C)3N4) As a stable compound with a graphite-like structure, the compound has the advantages of low price, good thermal stability and chemical stability, excellent photoelectrochemical property and the like,have been used in many ways. For example, in the field of photocatalysis, g-C3N4The method is mainly applied to photocatalytic water decomposition hydrogen production, photocatalytic organic pollutant degradation, photocatalytic organic synthesis and the like. Furthermore, in the field of electrochemistry, g-C3N4But also to electrocatalysis and electrochemical energy storage, etc. Studies have demonstrated that g-C, a novel electrocatalytic material, due to its unique nitrogen-containing structure3N4Has extremely high catalytic activity in oxygen reduction reaction. Furthermore, because of the large number of lone pairs, g-C3N4Good adsorption to polar molecules such as water and methanol, and perhaps a considerable degree of catalysis by the material on water electrolysis, oxygen reduction, and methanol cracking. However, due to conventional g-C3N4The bulk material has poor specific surface area and poor electronic conductivity, and thus the effect of the bulk material in the actual application of electrocatalysis is not ideal. Therefore, g-C having a high specific surface area and a high electron-conducting ability was developed3N4The material is the necessary way for promoting the application of the novel catalytic material in the electrochemical field at present.
From a material science perspective, the development of "nanostructures" is undoubtedly a more direct effective approach to enhance catalytic activity. The nano structure can endow the material with higher specific surface area, provide more adsorption sites and reaction sites and facilitate the improvement of catalytic performance. Despite the wide variety of g-C3N4The nano structure has more reports at present, but the g-C is related at home and abroad3N4The research work on quantum dots "is still very rare. From the perspective of catalytic science, the "composite structure" is really a broader and practical strategy for constructing a high-performance catalyst. In particular g-C with high specific surface area3N4The quantum dots being carried on a conductive carrier to form a composite structure, e.g. g-C3N4The quantum dot/graphene composite material (CN 201610451199.9) can remarkably improve g-C3N4The electronic conductivity and the catalytic performance of the material. However, the graphene material alone often has no catalytic activity, and only in the composite isActing only as a conductive support, the overall catalytic performance of such a composite is to be further improved.
At present, g-C3N4The quantum dots are generally mixed with nickel titanate and Bi2O3The photocatalytic performance of the composite material is improved by compounding the metal oxides, but the g-C is not shown3N4Quantum dots and novel high-efficiency electro-catalytic material NiCo capable of being applied to hydrogen production by water electrolysis, oxygen reduction and methanol oxidation2O4Reports of complexing to further improve its electrocatalytic performance.
Therefore, the development of a novel composite material with better electrocatalytic performance to further widen the application of the composite material in the electrocatalytic field has important research significance and application value.
Disclosure of Invention
The invention aims to overcome the defect of poor electrocatalytic performance of a composite material in the prior art, and provides a nickel cobaltate hollow sphere/carbon nitride quantum dot composite material. In the composite material provided by the invention, the carbon nitride quantum dots are of small-sized nano structures, so that the material utilization rate is high; the nickel cobaltate hollow spheres have the function of storing electrolyte; the nickel cobaltate hollow spheres and the carbon nitride quantum dots form a surface-dot structure distribution, have high electron/ion conductivity and excellent electrochemical catalytic performance, and can be widely applied to the field of electrochemical catalysis.
In order to achieve the purpose, the invention adopts the following technical scheme:
the nickel cobaltate hollow sphere/carbon nitride quantum dot composite material is prepared from the following components in parts by mol: 1mmol of 0.4-1.2 g nickel cobaltate NiCo2O4Hollow spheres and nitrogen carbide g-C3N4Quantum dots of said g-C3N4Quantum dots deposited on the NiCo2O4On the hollow ball.
The invention provides a novel composite material compounded by nickel cobaltate hollow spheres and carbon nitride quantum dots, wherein in the composite material provided by the invention, nickel cobaltate has a special hollow sphere structure and can play a role in storing electrolyte, and carbon nitride has a small-size quantum dot nanostructure, so that the utilization rate is very high; meanwhile, the carbon nitride quantum dots are discretely distributed on the surface of the nickel cobaltate hollow sphere, and the carbon nitride quantum dots can be fully contacted with each other and cannot be completely covered, so that the improvement of the conduction characteristics of electrons and ions is facilitated. The composite material provided by the invention has strong electronic conductivity and high electrocatalytic activity, and can be widely applied to the field of electrochemical catalysis.
Preferably, the NiCo in the composite material2O4Hollow spheres and g-C3N4The molar mass ratio of the quantum dots is as follows: 1mmol:0.8 g.
The preparation method of the composite material comprises the following steps:
s1: mixing a nickel source, a cobalt source and g-C3N4Dissolving the quantum dot precursor in an organic solution, dispersing, reacting at constant temperature, washing, filtering and drying to obtain NiCo2O4Hollow sphere/g-C3N4A quantum dot mixed precursor;
s2: mixing NiCo obtained in S12O4Hollow sphere/g-C3N4And oxidizing the quantum dot mixed precursor for 1-5 hours at the temperature of 300-500 ℃ to obtain the nickel cobaltate hollow sphere/carbon nitride quantum dot.
Said g-C in the present invention3N4The quantum dot precursor can be obtained by high-temperature treatment of a conventional nitrogen-carbon precursor, wherein the nitrogen-carbon precursor is a compound containing nitrogen and carbon elements, such as melamine, cyanuric chloride, cyanamide, dicyanodiamide, urea and the like. The nickel source and the cobalt source used in the invention are also common nickel sources and cobalt sources used in the prior art. The raw materials (nickel source, cobalt source and g-C) in the invention3N4Quantum dots) can be used according to the final product NiCo2O4Hollow sphere/g-C3N4And obtaining the dosage relation of the quantum dots.
In the prior art, NiCo2O4The hollow spheres are mainly prepared by a spherical template method, such as a carbon sphere template method (CN201410325633. X) and an oxide sphere template method (CN 201611112566.9), and the methods are complex in steps and high in cost, so that the application and popularization of the hollow spheres are greatly limited. For g-C3N4Quantum dots, at presentThe only preparation methods are the ultrasonic disruption method (CN 201610140951.8) and the concentrated acid corrosion method (CN 201510232437.2), and the methods have high energy consumption, complicated preparation process and low quantum dot yield, and are not suitable for large-scale production.
The invention develops a synchronous air heat treatment method, which obtains NiCo through constant temperature reaction2O4Hollow sphere/g-C3N4Quantum dot mixed precursor and control of NiCo2O4Hollow sphere/g-C3N4The composite material with strong conductivity and high electrocatalytic activity is obtained at the temperature and time of the oxidation treatment of the quantum dot mixed precursor; the preparation method is simple, and overcomes the defects of the prior NiCo2O4Hollow spheres and g-C3N4The quantum dots have the problems of complex steps, complex process, high cost, difficult batch production and the like, and can be used for batch production.
Preferably, said g-C3N4The quantum dot precursor is obtained by performing high-temperature heat treatment on a nitrogen-carbon precursor. More preferably, the temperature of the high-temperature heat treatment is 450-650 ℃, and the time is 1-5 h.
Preferably, the constant temperature reaction in the S1 is carried out at the temperature of 150-200 ℃ for 4-8 h.
Preferably, the nickel source is one or more of nickel nitrate, nickel acetate, nickel sulfate or nickel chloride.
Preferably, the cobalt source is one or more of cobalt nitrate, cobalt acetate, cobalt sulfate or cobalt chloride.
Conventional organic solvents can be used to disperse the nickel source, cobalt source and g-C3N4And (3) quantum dot precursors.
Preferably, the organic solvent in S1 is one or more of isopropanol, glycerol, ethylene glycol or ethanol.
Preferably, the oxidation treatment temperature in S2 is 400 ℃ and the time is 3 h.
The application of the nickel cobaltate hollow sphere/carbon nitride quantum dot composite material as a catalytic material in the electrochemical field is also within the protection scope of the invention.
Compared with the prior art, the invention has the following beneficial effects: in the composite material provided by the invention, the carbon nitride quantum dots are of small-sized nano structures, so that the material utilization rate is high; the nickel cobaltate hollow spheres have the function of storing electrolyte; the nickel cobaltate hollow spheres and the carbon nitride quantum dots form a surface-dot structure distribution, have high electron/ion conductivity and excellent electrochemical catalytic performance, and can be widely applied to the field of electrochemical catalysis.
Drawings
FIG. 1 shows NiCo as provided in example 12O4Hollow sphere/g-C3N4An X-ray diffraction pattern of the quantum dot composite;
FIG. 2 shows NiCo provided in example 12O4Hollow sphere/g-C3N4A scanning electron microscopy image of the quantum dot composite;
FIG. 3 is a NiCo sample provided in example 12O4Hollow sphere/g-C3N4Transmission electron microscopy of the quantum dot composite;
FIG. 4 is a graph of the methanol oxidation electrocatalytic AC impedance profile provided in example 1;
FIG. 5 is a methanol oxidation electrocatalytic cyclic voltammogram provided in example 1;
FIG. 6 shows NiCo provided in comparative example 12O4Hollow sphere/g-C3N4A scanning electron microscopy image of the quantum dot composite;
FIG. 7 shows NiCo provided in comparative example 22O4Hollow sphere/g-C3N4A scanning electron microscopy image of the quantum dot composite;
FIG. 8 is a NiCo sample from comparative example 32O4Hollow sphere/g-C3N4A scanning electron microscopy image of the quantum dot composite;
FIG. 9 is a NiCo sample provided in comparative example 42O4Hollow sphere/g-C3N4Scanning electron microscopy of quantum dot composites.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Example 1
This example provides a NiCo2O4Hollow sphere/g-C3N4Quantum dot composite material, NiCo in the composite electrode material2O4Hollow spheres and g-C3N4The molar mass ratio of the quantum dots is as follows: 1mmol:0.8g, prepared by the following preparation method:
placing 50g of urea in a ceramic crucible, covering the ceramic crucible with a cover, placing the ceramic crucible in a muffle furnace, and performing heat treatment at 550 ℃ for 2 hours to obtain a product g-C3N4And (3) quantum dot precursors.
0.25 mmol of nickel nitrate, 0.50 mmol of cobalt nitrate and 0.2g g-C3N4Dissolving and dispersing the quantum dot precursor by using 50ml of glycerol and 10ml of ethylene glycol, then adding the quantum dot precursor into a hydrothermal reaction kettle, carrying out constant-temperature reaction for 6 hours at the temperature of 180 ℃, and finally washing, filtering and drying to obtain the product NiCo2O4Hollow sphere/g-C3N4And (3) mixing the quantum dots with the precursor.
0.2g of NiCo2O4Hollow sphere/g-C3N4Putting the quantum dot mixed precursor into a ceramic crucible, putting a muffle furnace in an air environment, heating and oxidizing at 400 ℃ for 3h, and finally collecting a solid product which is NiCo2O4Hollow sphere/g-C3N4A quantum dot composite material.
As shown in FIGS. 1 to 3, NiCo prepared as described above2O4Hollow sphere/g-C3N4Quantum dot composite material of which NiCo2O4The diameter of the hollow sphere is about 350nm, g-C3N4The diameter of the quantum dot is about5nm, the specific surface area of the composite material is 72 m2g-1. The diameters of the hollow spheres and the quantum dots are smaller, the material utilization rate is higher, and the performance is better.
As shown in FIGS. 4 to 5, NiCo prepared as described above2O4Hollow sphere/g-C3N4The methanol oxidation electrocatalysis performance of the quantum dot composite material is excellent: the alternating current impedance shows that the resistance value is only 5.2 omega, and the cyclic voltammetry shows that the electrocatalytic performance of 1.6V is as high as 851A/g, which is the best performance reported in the literature at present.
Example 2
This example provides a NiCo2O4Hollow sphere/g-C3N4Quantum dot composite material, NiCo in the composite electrode material2O4Hollow spheres and g-C3N4The molar mass ratio of the quantum dots is as follows: 1mmol:0.8g, prepared by the following preparation method:
placing 50g of urea in a ceramic crucible, covering the ceramic crucible with a cover, placing the ceramic crucible in a muffle furnace, and performing heat treatment at 550 ℃ for 2 hours to obtain a product g-C3N4And (3) quantum dot precursors.
0.25 mmol of nickel nitrate, 0.50 mmol of cobalt nitrate and 0.2g g-C3N4Dissolving and dispersing the quantum dot precursor by using 50ml of glycerol and 10ml of ethylene glycol, then adding the quantum dot precursor into a hydrothermal reaction kettle, carrying out constant-temperature reaction for 6 hours at the temperature of 180 ℃, and finally washing, filtering and drying to obtain the product NiCo2O4Hollow sphere/g-C3N4And (3) mixing the quantum dots with the precursor.
0.2g of NiCo2O4Hollow sphere/g-C3N4Putting the quantum dot mixed precursor into a ceramic crucible, putting a muffle furnace in an air environment, heating and oxidizing at 300 ℃ for 3h, and finally collecting a solid product which is NiCo2O4Hollow sphere/g-C3N4A quantum dot composite material.
NiCo prepared as described above2O4Hollow sphere/g-C3N4Quantum dot composite material of which NiCo2O4The diameter of the hollow sphere is aboutIs 400nm, g-C3N4The diameter of the quantum dot is about 8nm, and the specific surface area of the composite material is 63 m2g-1. The resistance value of the alternating current impedance is 8.4 omega, and the electrocatalytic performance of the cyclic voltammetry 1.6V is 792A/g.
Example 3
This example provides a NiCo2O4Hollow sphere/g-C3N4Quantum dot composite material, NiCo in the composite electrode material2O4Hollow spheres and g-C3N4The molar mass ratio of the quantum dots is as follows: 1mmol:0.8g, prepared by the following preparation method:
placing 50g of urea in a ceramic crucible, covering the ceramic crucible with a cover, placing the ceramic crucible in a muffle furnace, and performing heat treatment at 550 ℃ for 2 hours to obtain a product g-C3N4And (3) quantum dot precursors.
0.25 mmol of nickel nitrate, 0.50 mmol of cobalt nitrate and 0.2g g-C3N4Dissolving and dispersing the quantum dot precursor by using 50ml of glycerol and 10ml of ethylene glycol, then adding the quantum dot precursor into a hydrothermal reaction kettle, carrying out constant-temperature reaction for 6 hours at the temperature of 180 ℃, and finally washing, filtering and drying to obtain the product NiCo2O4Hollow sphere/g-C3N4And (3) mixing the quantum dots with the precursor.
0.2g of NiCo2O4Hollow sphere/g-C3N4Putting the quantum dot mixed precursor into a ceramic crucible, putting a muffle furnace in an air environment, heating and oxidizing at 500 ℃ for 3h, and finally collecting a solid product which is NiCo2O4Hollow sphere/g-C3N4A quantum dot composite material.
NiCo prepared as described above2O4Hollow sphere/g-C3N4Quantum dot composite material of which NiCo2O4The diameter of the hollow sphere is about 300nm, g-C3N4The diameter of the quantum dot is about 4nm, and the specific surface area of the composite material is 69 m2g-1. The resistance value of the alternating current impedance is 6.7 omega, and the electrocatalytic performance of the cyclic voltammetry 1.6V is 814A/g.
Example 4
This example provides a NiCo2O4Hollow sphere/g-C3N4Quantum dot composite material, NiCo in the composite electrode material2O4Hollow spheres and g-C3N4The molar mass ratio of the quantum dots is as follows: 1mmol:0.8g, prepared by the following preparation method:
placing 50g of urea in a ceramic crucible, covering the ceramic crucible with a cover, placing the ceramic crucible in a muffle furnace, and performing heat treatment at 550 ℃ for 2 hours to obtain a product g-C3N4And (3) quantum dot precursors.
0.25 mmol of nickel nitrate, 0.50 mmol of cobalt nitrate and 0.2g g-C3N4Dissolving and dispersing the quantum dot precursor by using 50ml of glycerol and 10ml of ethylene glycol, then adding the quantum dot precursor into a hydrothermal reaction kettle, carrying out constant-temperature reaction for 6 hours at the temperature of 180 ℃, and finally washing, filtering and drying to obtain the product NiCo2O4Hollow sphere/g-C3N4And (3) mixing the quantum dots with the precursor.
0.2g of NiCo2O4Hollow sphere/g-C3N4Putting the quantum dot mixed precursor into a ceramic crucible, putting a muffle furnace in an air environment, heating and oxidizing at 400 ℃ for 1h, and finally collecting a solid product which is NiCo2O4Hollow sphere/g-C3N4A quantum dot composite material.
NiCo prepared as described above2O4Hollow sphere/g-C3N4Quantum dot composite material of which NiCo2O4The diameter of the hollow sphere is about 450nm, g-C3N4The diameter of the quantum dot is about 10nm, and the specific surface area of the composite material is 57 m2g-1. The resistance value of the alternating current impedance is 9.5 omega, and the electrocatalytic performance of the cyclic voltammetry 1.6V is 720A/g.
Example 5
This example provides a NiCo2O4Hollow sphere/g-C3N4Quantum dot composite material, NiCo in the composite electrode material2O4Hollow spheres and g-C3N4The molar mass ratio of the quantum dots is as follows: 1mmol:0.8g, prepared by the following preparation method:
50g of urea was placed in a ceramic crucible and covered with a lidCovering, placing in a muffle furnace for heat treatment at 550 ℃ for 2h to obtain the product g-C3N4And (3) quantum dot precursors.
0.25 mmol of nickel nitrate, 0.50 mmol of cobalt nitrate and 0.2g g-C3N4Dissolving and dispersing the quantum dot precursor by using 50ml of glycerol and 10ml of ethylene glycol, then adding the quantum dot precursor into a hydrothermal reaction kettle, carrying out constant-temperature reaction for 6 hours at the temperature of 180 ℃, and finally washing, filtering and drying to obtain the product NiCo2O4Hollow sphere/g-C3N4And (3) mixing the quantum dots with the precursor.
0.2g of NiCo2O4Hollow sphere/g-C3N4Putting the quantum dot mixed precursor into a ceramic crucible, putting a muffle furnace in an air environment, heating and oxidizing at 400 ℃ for 5h, and finally collecting a solid product which is NiCo2O4Hollow sphere/g-C3N4A quantum dot composite material.
NiCo prepared as described above2O4Hollow sphere/g-C3N4Quantum dot composite material of which NiCo2O4The diameter of the hollow sphere is about 280nm, g-C3N4The diameter of the quantum dot is about 3nm, and the specific surface area of the composite material is 70 m2g-1. The resistance value of the alternating current impedance is 5.3 omega, and the electrocatalytic performance of the cyclic voltammetry 1.6V is 834A/g.
Example 6
This example provides a NiCo2O4Hollow sphere/g-C3N4Quantum dot composite material, NiCo in the composite electrode material2O4Hollow spheres and g-C3N4The molar mass ratio of the quantum dots is as follows: 1mmol:0.8g, prepared by the following preparation method:
placing 50g of urea in a ceramic crucible, covering with a cover, placing in a muffle furnace, and performing heat treatment at 450 deg.C for 5h to obtain g-C product3N4And (3) quantum dot precursors.
0.25 mmol of nickel acetate, 0.50 mmol of cobalt acetate and 0.2g g-C3N4The quantum dot precursor was dissolved and dispersed with 50ml glycerol and 10ml ethylene glycol, followed by addition of waterA thermal reaction kettle is used for carrying out constant temperature reaction for 6 hours at the temperature of 180 ℃, and finally, the product NiCo is obtained by washing, filtering and drying2O4Hollow sphere/g-C3N4And (3) mixing the quantum dots with the precursor.
0.2g of NiCo2O4Hollow sphere/g-C3N4Putting the quantum dot mixed precursor into a ceramic crucible, putting a muffle furnace in an air environment, heating and oxidizing at 400 ℃ for 3h, and finally collecting a solid product which is NiCo2O4Hollow sphere/g-C3N4A quantum dot composite material.
NiCo prepared as described above2O4Hollow sphere/g-C3N4Quantum dot composite material of which NiCo2O4The diameter of the hollow sphere is about 550nm, g-C3N4The diameter of the quantum dot is about 5nm, and the specific surface area of the composite material is 61 m2g-1. The resistance value of the alternating current impedance is 7.8 omega, and the electrocatalytic performance of the cyclic voltammetry 1.6V is 743A/g.
Example 7
This example provides a NiCo2O4Hollow sphere/g-C3N4Quantum dot composite material, NiCo in the composite electrode material2O4Hollow spheres and g-C3N4The molar mass ratio of the quantum dots is as follows: 1mmol:0.8g, prepared by the following preparation method:
placing 50g of melamine in a ceramic crucible, covering with a cover, placing in a muffle furnace, and performing heat treatment at 650 deg.C for 1h to obtain g-C3N4And (3) quantum dot precursors.
0.25 mmol of nickel sulfate, 0.50 mmol of cobalt sulfate and 0.2g g-C3N4Dissolving and dispersing the quantum dot precursor by using 50ml of glycerol and 10ml of ethylene glycol, then adding the quantum dot precursor into a hydrothermal reaction kettle, carrying out constant-temperature reaction for 8 hours at the temperature of 100 ℃, and finally washing, filtering and drying to obtain the product NiCo2O4Hollow sphere/g-C3N4And (3) mixing the quantum dots with the precursor.
0.2g of NiCo2O4Hollow sphere/g-C3N4Before quantum dot mixingThe driver body is placed in a ceramic crucible, a muffle furnace is placed in an air environment, heating and oxidation treatment is carried out for 3 hours at 400 ℃, and finally, a solid product is collected to be NiCo2O4Hollow sphere/g-C3N4A quantum dot composite material.
NiCo prepared as described above2O4Hollow sphere/g-C3N4Quantum dot composite material of which NiCo2O4The diameter of the hollow sphere is about 500nm, g-C3N4The diameter of the quantum dot is about 5nm, and the specific surface area of the composite material is 63 m2g-1. The resistance value of the alternating current impedance is 8.0 omega, and the electrocatalytic performance of the cyclic voltammetry 1.6V is 726A/g.
Example 8
This example provides a NiCo2O4Hollow sphere/g-C3N4Quantum dot composite material, NiCo in the composite electrode material2O4Hollow spheres and g-C3N4The molar mass ratio of the quantum dots is as follows: 1mmol:0.8g, prepared by the following preparation method:
placing 50g of urea in a ceramic crucible, covering the ceramic crucible with a cover, placing the ceramic crucible in a muffle furnace, and performing heat treatment at 550 ℃ for 2 hours to obtain a product g-C3N4And (3) quantum dot precursors.
0.25 mmol of nickel chloride, 0.50 mmol of cobalt chloride and 0.2g g-C3N4Dissolving and dispersing the quantum dot precursor by using 50ml of glycerol and 10ml of ethylene glycol, then adding the quantum dot precursor into a hydrothermal reaction kettle, carrying out constant-temperature reaction for 4 hours at the temperature of 200 ℃, and finally washing, filtering and drying to obtain the product NiCo2O4Hollow sphere/g-C3N4And (3) mixing the quantum dots with the precursor.
0.2g of NiCo2O4Hollow sphere/g-C3N4Putting the quantum dot mixed precursor into a ceramic crucible, putting a muffle furnace in an air environment, heating and oxidizing at 400 ℃ for 3h, and finally collecting a solid product which is NiCo2O4Hollow sphere/g-C3N4A quantum dot composite material.
NiCo prepared as described above2O4Hollow sphere/g-C3N4Quantum dot composite material of which NiCo2O4The diameter of the hollow sphere is about 700nm, g-C3N4The diameter of the quantum dot is about 6nm, and the specific surface area of the composite material is 55 m2g-1. The resistance value of the alternating current impedance is 8.6 omega, and the electrocatalytic performance of the cyclic voltammetry 1.6V is 695A/g.
Example 9
This example provides a NiCo2O4Hollow sphere/g-C3N4Quantum dot composite material, NiCo in the composite electrode material2O4Hollow spheres and g-C3N4The molar mass ratio of the quantum dots is as follows: 1mmol:0.4g, prepared by the following preparation method:
placing 50g of urea in a ceramic crucible, covering the ceramic crucible with a cover, placing the ceramic crucible in a muffle furnace, and performing heat treatment at 550 ℃ for 2 hours to obtain a product g-C3N4And (3) quantum dot precursors.
0.25 mmol of nickel nitrate, 0.50 mmol of cobalt nitrate and 0.1g g-C3N4Dissolving and dispersing the quantum dot precursor by using 50ml of glycerol and 10ml of ethylene glycol, then adding the quantum dot precursor into a hydrothermal reaction kettle, carrying out constant-temperature reaction for 6 hours at the temperature of 180 ℃, and finally washing, filtering and drying to obtain the product NiCo2O4Hollow sphere/g-C3N4And (3) mixing the quantum dots with the precursor.
0.2g of NiCo2O4Hollow sphere/g-C3N4Putting the quantum dot mixed precursor into a ceramic crucible, putting a muffle furnace in an air environment, heating and oxidizing at 400 ℃ for 3h, and finally collecting a solid product which is NiCo2O4Hollow sphere/g-C3N4A quantum dot composite material.
NiCo prepared as described above2O4Hollow sphere/g-C3N4Quantum dot composite material of which NiCo2O4The diameter of the hollow sphere is about 350nm, g-C3N4The diameter of the quantum dot is about 4nm, and the specific surface area of the composite material is 70 m2g-1. The resistance value of the alternating current impedance is 5.7 omega, and the electrocatalytic performance of the cyclic voltammetry 1.6V is 708A/g.
Example 10
This example provides a NiCo2O4Hollow sphere/g-C3N4Quantum dot composite material, NiCo in the composite electrode material2O4Hollow spheres and g-C3N4The molar mass ratio of the quantum dots is as follows: 1mmol:1.2g, prepared by the following preparation method:
placing 50g of urea in a ceramic crucible, covering the ceramic crucible with a cover, placing the ceramic crucible in a muffle furnace, and performing heat treatment at 550 ℃ for 2 hours to obtain a product g-C3N4And (3) quantum dot precursors.
0.25 mmol of nickel nitrate, 0.50 mmol of cobalt nitrate and 0.3g g-C3N4Dissolving and dispersing the quantum dot precursor by using 50ml of glycerol and 10ml of ethylene glycol, then adding the quantum dot precursor into a hydrothermal reaction kettle, carrying out constant-temperature reaction for 6 hours at the temperature of 180 ℃, and finally washing, filtering and drying to obtain the product NiCo2O4Hollow sphere/g-C3N4And (3) mixing the quantum dots with the precursor.
0.2g of NiCo2O4Hollow sphere/g-C3N4Putting the quantum dot mixed precursor into a ceramic crucible, putting a muffle furnace in an air environment, heating and oxidizing at 400 ℃ for 3h, and finally collecting a solid product which is NiCo2O4Hollow sphere/g-C3N4A quantum dot composite material.
NiCo prepared as described above2O4Hollow sphere/g-C3N4Quantum dot composite material of which NiCo2O4The diameter of the hollow sphere is about 350nm, g-C3N4The diameter of the quantum dot is about 7nm, and the specific surface area of the composite material is 64 m2g-1. The resistance value of the alternating current impedance is 5.4 omega, and the electrocatalytic performance of the cyclic voltammetry 1.6V is 759A/g.
Comparative example 1
This comparative example provides a NiCo2O4Hollow sphere/g-C3N4Quantum dot composite material, NiCo in the composite electrode material2O4Hollow spheres and g-C3N4The molar mass ratio of the quantum dots is as follows: 1mmol:2.4g, and the preparation method is as follows:
placing 50g of urea in a ceramic crucible, covering the ceramic crucible with a cover, placing the ceramic crucible in a muffle furnace, and performing heat treatment at 550 ℃ for 2 hours to obtain a product g-C3N4And (3) quantum dot precursors.
0.25 mmol of nickel nitrate, 0.50 mmol of cobalt nitrate and 0.6g g-C3N4Dissolving and dispersing the quantum dot precursor by using 50ml of glycerol and 10ml of ethylene glycol, then adding the quantum dot precursor into a hydrothermal reaction kettle, carrying out constant-temperature reaction for 6 hours at the temperature of 180 ℃, and finally washing, filtering and drying to obtain the product NiCo2O4Hollow sphere/g-C3N4And (3) mixing the quantum dots with the precursor.
0.2g of NiCo2O4Hollow sphere/g-C3N4Putting the quantum dot mixed precursor into a ceramic crucible, putting a muffle furnace in an air environment, heating and oxidizing at 400 ℃ for 3h, and finally collecting a solid product which is NiCo2O4Hollow sphere/g-C3N4A quantum dot composite material.
As shown in FIG. 6, NiCo prepared as described above2O4Hollow sphere/g-C3N4Quantum dot composite material of which NiCo2O4The diameter of the hollow sphere is about 390 nm, g-C3N4The diameter of the quantum dot is about 30 nm (the particle size is overlarge due to overhigh content of the precursor), the surface of the hollow sphere is completely covered, and the specific surface area of the composite material is 45m2g-1. The resistance value of the alternating current impedance is 14.8 omega, and the electrocatalytic performance of the cyclic voltammetry 1.6V is 532A/g.
Comparative example 2
This comparative example provides a NiCo2O4Hollow sphere/g-C3N4Quantum dot composite material, NiCo in the composite electrode material2O4Hollow spheres and g-C3N4The molar mass ratio of the quantum dots is as follows: 02g of 1mmol, and the preparation method is as follows:
placing 50g of urea in a ceramic crucible, covering the ceramic crucible with a cover, placing the ceramic crucible in a muffle furnace, and performing heat treatment at 550 ℃ for 2 hours to obtain a product g-C3N4And (3) quantum dot precursors.
Adding 0.25 mmol of nitric acidNickel, 0.50 mmol of cobalt nitrate and 0.05g g-C3N4Dissolving and dispersing the quantum dot precursor by using 50ml of glycerol and 10ml of ethylene glycol, then adding the quantum dot precursor into a hydrothermal reaction kettle, carrying out constant-temperature reaction for 6 hours at the temperature of 180 ℃, and finally washing, filtering and drying to obtain the product NiCo2O4Hollow sphere/g-C3N4And (3) mixing the quantum dots with the precursor.
0.2g of NiCo2O4Hollow sphere/g-C3N4Putting the quantum dot mixed precursor into a ceramic crucible, putting a muffle furnace in an air environment, heating and oxidizing at 400 ℃ for 3h, and finally collecting a solid product which is NiCo2O4Hollow sphere/g-C3N4A quantum dot composite material.
NiCo prepared as described above, FIG. 72O4Hollow sphere/g-C3N4Quantum dot composite material of which NiCo2O4The diameter of the hollow sphere is about 420 nm, and g-C is not existed3N4Quantum dot generation (little oxidation product is left due to low precursor content), and the specific surface area of the composite material is 35m2g-1. The resistance value of the alternating current impedance is 8.2 omega, and the electrocatalytic performance of the cyclic voltammetry 1.6V is 386A/g.
Comparative example 3
This comparative example provides a NiCo2O4Hollow sphere/g-C3N4Quantum dot composite material, NiCo in the composite electrode material2O4Hollow spheres and g-C3N4The molar mass ratio of the quantum dots is as follows: 1.25mmol:1g, prepared by the following preparation method:
placing 50g of urea in a ceramic crucible, covering the ceramic crucible with a cover, placing the ceramic crucible in a muffle furnace, and performing heat treatment at 550 ℃ for 2 hours to obtain a product g-C3N4And (3) quantum dot precursors.
0.25 mmol of nickel nitrate, 0.50 mmol of cobalt nitrate and 0.2g g-C3N4Dissolving and dispersing the quantum dot precursor by using 50ml of glycerol and 10ml of ethylene glycol, then adding the quantum dot precursor into a hydrothermal reaction kettle, carrying out constant-temperature reaction for 6 hours at the temperature of 180 ℃, and finally washing, filtering and drying to obtain the product NiCo2O4Hollow sphere/g-C3N4And (3) mixing the quantum dots with the precursor.
0.2g of NiCo2O4Hollow sphere/g-C3N4Putting the quantum dot mixed precursor into a ceramic crucible, putting a muffle furnace in an air environment, heating and oxidizing at 200 ℃ for 3h, and finally collecting a solid product which is NiCo2O4Hollow sphere/g-C3N4A quantum dot composite material.
As shown in FIG. 8, NiCo prepared as described above2O4Hollow sphere/g-C3N4Quantum dot composite material of which NiCo2O4The diameter of the hollow sphere is about 450nm, and g-C is not existed3N4Quantum dot formation with only large chunks of g-C3N4The sheet (the heating oxidation temperature is too low to etch the precursor into quantum dots), and the specific surface area of the composite material is 30 m2g-1. The resistance value of the alternating current impedance is 39.4 omega, and the electrocatalytic performance of the cyclic voltammetry 1.6V is 486A/g.
Comparative example 4
This comparative example provides a NiCo2O4Hollow sphere/g-C3N4Quantum dot composite material, NiCo in the composite electrode material2O4Hollow spheres and g-C3N4The molar mass ratio of the quantum dots is as follows: 1.25mmol:1g, prepared by the following preparation method:
placing 50g of urea in a ceramic crucible, covering the ceramic crucible with a cover, placing the ceramic crucible in a muffle furnace, and performing heat treatment at 550 ℃ for 2 hours to obtain a product g-C3N4And (3) quantum dot precursors.
0.25 mmol of nickel nitrate, 0.50 mmol of cobalt nitrate and 0.2g g-C3N4Dissolving and dispersing the quantum dot precursor by using 50ml of glycerol and 10ml of ethylene glycol, then adding the quantum dot precursor into a hydrothermal reaction kettle, carrying out constant-temperature reaction for 6 hours at the temperature of 180 ℃, and finally washing, filtering and drying to obtain the product NiCo2O4Hollow sphere/g-C3N4And (3) mixing the quantum dots with the precursor.
0.2g of NiCo2O4Hollow sphere/g-C3N4Quantum dot mixturePutting the combined precursor in a ceramic crucible, putting the ceramic crucible in a muffle furnace in an air environment, heating and oxidizing for 3h at 600 ℃, and finally collecting a solid product NiCo2O4Hollow sphere/g-C3N4A quantum dot composite material.
NiCo prepared as described above, FIG. 92O4Hollow sphere/g-C3N4Quantum dot composite material of which NiCo2O4The diameter of the hollow sphere is about 350nm, the sphericity is poor (the precursor structure collapses due to overhigh heating oxidation temperature), and the g-C is not existed3N4Quantum dot generation (the precursor is completely oxidized and decomposed due to too high heating and oxidation temperature), and the specific surface area of the composite material is 32 m2g-1. The resistance value of the alternating current impedance is 7.8 omega, and the electrocatalytic performance of the cyclic voltammetry 1.6V is 521A/g.

Claims (9)

1. The nickel cobaltate hollow sphere/carbon nitride quantum dot composite material is characterized by comprising the following components in molar mass ratio: 1mmol of 0.4-1.2 g nickel cobaltate NiCo2O4Hollow spheres and nitrogen carbide g-C3N4Quantum dots of said g-C3N4Quantum dots are deposited and distributed on the NiCo discretely2O4On the hollow ball.
2. The nickel cobaltate hollow sphere/carbon nitride quantum dot composite material of claim 1, wherein NiCo in the composite material2O4Hollow spheres and g-C3N4The molar mass ratio of the quantum dots is as follows: 1mmol:0.8 g.
3. A method for preparing a composite material according to any one of claims 1 to 2, characterized in that the method comprises the steps of:
s1: mixing a nickel source, a cobalt source and g-C3N4Dissolving the quantum dot precursor in an organic solution, dispersing, reacting at constant temperature, washing, filtering and drying to obtain NiCo2O4Hollow sphere/g-C3N4A quantum dot mixed precursor;
S2: mixing NiCo obtained in S12O4Hollow sphere/g-C3N4And oxidizing the quantum dot mixed precursor for 1-5 hours at the temperature of 300-500 ℃ to obtain the nickel cobaltate hollow sphere/carbon nitride quantum dot.
4. The method for preparing a composite material according to claim 3, wherein said g-C is3N4The quantum dot precursor is obtained by performing high-temperature heat treatment on a nitrogen-carbon precursor.
5. The preparation method of the composite material according to claim 3, wherein the isothermal reaction in the S1 is carried out at a temperature of 150-200 ℃ for 4-8 h.
6. The method for preparing the composite material according to claim 3, wherein the nickel source is one or more of nickel nitrate, nickel acetate, nickel sulfate or nickel chloride.
7. The method for preparing the composite material according to claim 3, wherein the cobalt source is one or more of cobalt nitrate, cobalt acetate, cobalt sulfate or cobalt chloride.
8. The method for preparing a composite material according to claim 3, wherein the oxidation treatment in S2 is performed at 400 ℃ for 3 hours.
9. The application of the nickel cobaltate hollow sphere/carbon nitride quantum dot composite material as a catalytic material in the electrochemical field.
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