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 PDFInfo
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 192
- 239000002131 composite material Substances 0.000 title claims abstract description 116
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 31
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910003266 NiCo Inorganic materials 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims description 85
- 229910005949 NiCo2O4 Inorganic materials 0.000 claims description 79
- 238000010438 heat treatment Methods 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 15
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 13
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007833 carbon precursor Substances 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 abstract 3
- 239000000919 ceramic Substances 0.000 description 51
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 45
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 45
- 239000000047 product Substances 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 238000002484 cyclic voltammetry Methods 0.000 description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 14
- 239000004202 carbamide Substances 0.000 description 14
- 239000007772 electrode material Substances 0.000 description 14
- 239000012265 solid product Substances 0.000 description 14
- 238000001027 hydrothermal synthesis Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000004626 scanning electron microscopy Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 239000013590 bulk material Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- DGXKDBWJDQHNCI-UHFFFAOYSA-N dioxido(oxo)titanium nickel(2+) Chemical compound [Ni++].[O-][Ti]([O-])=O DGXKDBWJDQHNCI-UHFFFAOYSA-N 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
本发明涉及一种钴酸镍空心球/氮化碳量子点复合材料及其制备方法和应用。所述复合材料由摩尔质量比为1mmol:0.4~1.2g的钴酸镍NiCo2O4空心球和碳化氮g‑C3N4量子点制成，所述g‑C3N4量子点沉积在所述NiCo2O4空心球上。本发明提供的复合材料中，氮化碳量子点为小尺寸的纳米结构，材料利用率高；钴酸镍空心球具备存储电解液的功能；钴酸镍空心球和氮化碳量子点形成面‑点结构分布，电子/离子导电较高，电化学催化性能优异，可广泛应用于电化学催化领域。
The invention relates to a nickel cobalt oxide hollow sphere/carbon nitride quantum dot composite material and a preparation method and application thereof. The composite material is made of nickel cobaltate NiCo 2 O 4 hollow spheres with a molar mass ratio of 1 mmol: 0.4 to 1.2 g and carbon nitride g-C 3 N 4 quantum dots, and the g-C 3 N 4 quantum dots are deposited on the NiCo 2 O 4 hollow spheres. In the composite material provided by the invention, the carbon nitride quantum dots are small-sized nanostructures, and the material utilization rate is high; the nickel cobalt oxide hollow spheres have the function of storing electrolyte; the nickel cobalt oxide hollow spheres and the carbon nitride quantum dots form a surface ‑Dot structure distribution, high electron/ionic conductivity, and excellent electrochemical catalytic performance, which can be widely used in the field of electrochemical catalysis.
Description
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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| CN105642332B (en) * | 2016-03-15 | 2018-09-21 | 辽宁大学 | A kind of g-C3N4/TiO2Composite photo-catalyst and preparation method thereof |
| US10413966B2 (en) * | 2016-06-20 | 2019-09-17 | Baker Hughes, A Ge Company, Llc | Nanoparticles having magnetic core encapsulated by carbon shell and composites of the same |
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| CN107233907A (en) * | 2017-06-26 | 2017-10-10 | 南昌航空大学 | A kind of method that a step prepares height hydridization azotized carbon nano piece/titanium dioxide hollow ball hetero-junctions |
| CN107345931B (en) * | 2017-07-10 | 2019-08-27 | 山东利源康赛环境咨询有限责任公司 | It is a kind of based on carbonitride-binary metal boron oxide compound composite material bisphenol-A optical electro-chemistry sensor and its preparation and application |
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