CN114427103B - Hexagonal boron nitride nanosheet-reduced graphene oxide composite material-based electrocatalyst, and preparation method and application thereof - Google Patents
Hexagonal boron nitride nanosheet-reduced graphene oxide composite material-based electrocatalyst, and preparation method and application thereof Download PDFInfo
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- CN114427103B CN114427103B CN202210104267.XA CN202210104267A CN114427103B CN 114427103 B CN114427103 B CN 114427103B CN 202210104267 A CN202210104267 A CN 202210104267A CN 114427103 B CN114427103 B CN 114427103B
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 110
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 109
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000002131 composite material Substances 0.000 title claims abstract description 74
- 239000002135 nanosheet Substances 0.000 title claims abstract description 67
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 10
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- 238000000034 method Methods 0.000 claims abstract description 7
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- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 230000001808 coupling effect Effects 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000006185 dispersion Substances 0.000 description 15
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- 230000003197 catalytic effect Effects 0.000 description 12
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- 238000001228 spectrum Methods 0.000 description 7
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
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- 239000000084 colloidal system Substances 0.000 description 3
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- 238000010438 heat treatment Methods 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
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- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 239000011812 mixed powder Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009812 interlayer coupling reaction Methods 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention provides an electrocatalyst based on a hexagonal boron nitride nanosheet-reduced graphene oxide composite material, and a preparation method and application thereof, and belongs to the technical field of new materials. According to the invention, the hexagonal boron nitride nanosheet-reduced graphene oxide composite material is used as an electrocatalytic material, a hydrothermal synthesis method is utilized to enable the composite material to generate a large number of defect sites, a freeze drying method is utilized to enable the composite material to generate a planar heterostructure, and through coupling action of the hexagonal boron nitride nanosheets and the reduced graphene oxide interlayer defect sites, the reaction overpotential is effectively reduced, the electrocatalytic efficiency is improved, and the composite material has good stability and can be used as a metal-free catalyst in electrocatalytic oxygen reduction reaction.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to an electrocatalyst based on hexagonal boron nitride nanosheets-reduced graphene oxide composite materials, and a preparation method and application thereof.
Background
The hydrogen energy is a clean energy widely accepted in the world at present, the current hydrogen acquisition mode mainly comprises electrolyzed water, and the electrolyzed water reaction mainly comprises a cathode hydrogen evolution reaction (HER reaction) and an anode oxygen evolution reaction (OER reaction). The oxygen evolution reaction consists of a four-electron transfer process, and the high overpotential in the reaction has poor material circulation stability, so that the efficiency of electrocatalytic oxygen evolution is limited, and the development of an efficient and stable oxygen evolution reaction electrocatalyst is needed.
The existing noble metal oxygen evolution reaction catalysts represented by iridium oxide and ruthenium oxide have high activity, but the activity is reduced at a high temperature, and noble metal resources are limited and the cost is high, so that the noble metal oxygen evolution reaction catalysts cannot be used on a large scale. Therefore, on the premise of keeping good catalytic effect, partial replacement or total replacement of noble metals, and searching for other high-performance and low-cost catalytic materials have become a research hotspot. Considering the cost, source and practical convenience of the catalytic material, carbon-based catalytic materials are becoming a trend because of low price and high thermal stability. In particular, two-dimensional materials such as graphene, boron nitride and molybdenum disulfide have been found to be seen as two-dimensional layered materials at the atomic level. Graphene and boron nitride are used as outstanding representatives in two-dimensional materials, and have the advantages of large specific surface area, multiple active sites, simple synthesis process and the like, so that the graphene and the boron nitride become an ideal catalyst to be applied to hydrogen production by water electrolysis. However, in actual operation, graphene has a zero band gap structure and high conductivity, but has poor stability in chemical catalytic reaction; hexagonal boron nitride has extremely excellent chemical stability and thermal stability, but due to its ultra-wide band gap, electrical insulation is also a major factor impeding its use in electrocatalytic reactions. Thus, it is an entirely new challenge to enable hexagonal boron nitride and graphene composites to develop new properties in the absence of metal catalysts.
At present, a document reports that a hexagonal boron nitride/graphene composite material is prepared by a hydrothermal method, mainly a nitride precursor and graphene oxide are mixed and then subjected to a hydrothermal synthesis reaction, so that the hexagonal boron nitride/reduced graphene oxide composite material is finally formed. However, the hexagonal boron nitride/reduced graphene oxide composite material formed by the method is not pure enough and has lower quality, and a plurality of incompletely reacted precursors exist to cause lower catalytic efficiency. In conclusion, the prepared hexagonal boron nitride-reduced graphene oxide composite material electrocatalyst has the characteristics, and can surpass and improve the weaknesses of the electrocatalyst, so that the electrocatalyst performance of the electrocatalyst is improved.
Disclosure of Invention
In view of the above, the invention aims to provide an electrocatalyst based on hexagonal boron nitride nanosheets-reduced graphene oxide composite materials, and a preparation method and application thereof. The electrocatalyst based on the hexagonal boron nitride nanosheet-reduced graphene oxide composite material provided by the invention has the advantages of low cost and good catalytic performance. And the preparation method is simple, and is favorable for forming industrialized production.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an electrocatalyst based on a hexagonal boron nitride nanosheet-reduced graphene oxide composite material, which is prepared from hexagonal boron nitride nanosheets-reduced graphene oxide, and is characterized in that the diameter of the hexagonal boron nitride nanosheets is 1-10 mu m, and the hexagonal boron nitride nanosheets are uniformly dispersed on a graphene plane; the diameter of the reduced graphene oxide is 50-100 mu m, the hexagonal boron nitride nanosheets and the reduced graphene oxide are in a plane heterostructure and are coupled by interlayer van der Waals acting force, and the composite material has a large number of defect sites, does not contain additional introduced functional groups and does not contain any metal catalyst; the mass ratio of the graphene oxide to the hexagonal boron nitride nanosheets can be 1:1-1:7.
The invention provides a preparation method of an electrocatalyst based on a hexagonal boron nitride nanosheet-reduced graphene oxide composite material, which is characterized in that,
(1) And respectively measuring graphene oxide dispersion liquid (0.5-1 mg/mL diluted in deionized water) and hexagonal boron nitride nanosheet powder, dispersing in deionized water, stirring, and performing ultrasonic treatment on the stirred dispersion liquid to obtain a dispersion liquid containing few layers of boron nitride nanosheets and graphene oxide.
(2) And (3) filling the dispersion liquid into a reaction kettle with polytetrafluoroethylene as a lining, and putting the reaction kettle into an oven for reaction. And (3) putting the colloid after the reaction into a freeze dryer for drying to constant weight, and obtaining the hexagonal boron nitride nanosheet-reduced graphene oxide composite material.
(3) Dispersing the electrocatalyst in a solvent by ultrasonic waves to obtain pasty slurry;
(4) The electrocatalytic electrode may be prepared by applying the paste slurry to the surface of the electrocatalytic electrode element and drying.
Preferably, the solvent in the step (3) is a mixed solution of teflon (nafion) and isopropanol.
Preferably, in the step (3), the ratio of the mass of the electrocatalyst material to the volume of the solvent is 5 to 6mg:1mL.
The invention also provides application of the hexagonal boron nitride nanosheet-reduced graphene oxide composite material-based electrocatalyst in electrocatalytic oxygen reduction.
The beneficial effects of the invention are as follows:
1. according to the hexagonal boron nitride nano sheet-reduced graphene oxide composite material, hexagonal boron nitride nano sheets and graphene oxide are used as raw materials, the hexagonal boron nitride nano sheets are uniformly distributed on the surface of a graphene thin layer in a hydrothermal synthesis mode, meanwhile, the hexagonal boron nitride nano sheets and the graphene are more easily combined, defect sites are obvious, and the hexagonal boron nitride nano sheets-reduced graphene oxide composite material with uniformly distributed sheets is beneficial to improving the performance of a catalyst.
2. The hexagonal boron nitride nanosheet-reduced graphene oxide based composite material has more defect active sites and good conductivity, and in addition, the catalytic performance of the composite material is further improved through the strong coupling effect of double-lamellar defect sites, and the electron transfer resistance is reduced, so that the prepared catalytic material has higher oxygen evolution activity and stability.
3. The invention provides the preparation method of the hexagonal boron nitride nanosheet-reduced graphene oxide composite material, which is simple to operate, low in cost and easy to realize industrial production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is a full spectrum of X-ray photoelectron spectra of hexagonal boron nitride nanoplatelets-graphene oxide composites, hexagonal boron nitride nanoplatelets, and reduced graphene oxide prepared in examples 1-3 and comparative example 1;
FIG. 2 is an X-ray photoelectron spectroscopy core electron spectrum of the hexagonal boron nitride nanoplatelet-reduced graphene oxide composite material prepared in example 1;
FIG. 3 is an X-ray photoelectron spectroscopy core electron spectrum of the hexagonal boron nitride nanoplatelet-reduced graphene oxide composite material prepared in example 2;
FIG. 4 is an X-ray photoelectron spectroscopy core electron spectrum of the hexagonal boron nitride nanoplatelet-reduced graphene oxide composite material prepared in example 3;
FIG. 5 is a scanning electron micrograph (a: low magnification; b: high magnification) of a hexagonal boron nitride nanoplatelet-reduced graphene oxide composite material prepared in example 2;
FIG. 6 is a transmission electron microscope image of the hexagonal boron nitride nanoplatelets-reduced graphene oxide composite material prepared in example 2;
FIG. 7 is an electrochemical linear scan voltammogram of the hexagonal boron nitride nanoplatelets-graphene oxide composite material, hexagonal boron nitride nanoplatelets, and reduced graphene oxide obtained in example 2;
FIG. 8 is an electrochemical Tafil slope plot of the hexagonal boron nitride nanoplatelets-graphene oxide composite material, hexagonal boron nitride nanoplatelets, and reduced graphene oxide obtained in example 2;
FIG. 9 is an electrochemical AC impedance plot of the hexagonal boron nitride nanoplatelets-graphene oxide composite material, hexagonal boron nitride nanoplatelets, and reduced graphene oxide obtained in example 2;
fig. 10 is a graph showing the electrochemical stability of the hexagonal boron nitride nanoplatelet-graphene oxide composite material obtained in example 2 compared with that of reduced graphene oxide.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. Embodiments of the invention and features of the embodiments may be combined with each other without conflict.
The invention provides a preparation method of an electrocatalyst based on hexagonal boron nitride nanosheets-reduced graphene oxide composite materials, which comprises the following steps:
(1) And respectively measuring graphene oxide dispersion liquid (0.5-1 mg/mL diluted in deionized water) and hexagonal boron nitride nanosheet powder, dispersing in deionized water, stirring, and performing ultrasonic treatment on the stirred dispersion liquid to obtain a dispersion liquid containing few layers of boron nitride nanosheets and graphene oxide.
(2) And (3) filling the dispersion liquid into a reaction kettle with polytetrafluoroethylene as a lining, and putting the reaction kettle into an oven for reaction. And (3) putting the colloid after the reaction into a freeze dryer for drying to constant weight, and obtaining the hexagonal boron nitride nanosheet-reduced graphene oxide composite material.
(3) Fully grinding the hexagonal boron nitride nanosheet-reduced graphene oxide composite material, and ultrasonically dispersing the ground composite material in a solvent to obtain pasty slurry;
(4) And coating the pasty slurry on the surface of foam nickel and drying to obtain the electrocatalytic working electrode.
In an embodiment of the present invention, the mass ratio of the reduced graphene oxide to the hexagonal boron nitride in the step (1) may be controlled to be 1:1 to 1:7, specifically may be 1:1,1:2,1:3,1:4,1:5,1:6,1:7, etc.
In an embodiment of the present invention, the solvent in the step (3) is a mixed solution of deionized water, teflon (nafion) and isopropyl alcohol, and a solvent volume ratio of deionized water to isopropyl alcohol is preferably 500-750 μl: 250. Mu.L, more preferably 750. Mu.L: 250 μl; the volume of the Teflon solvent is preferably 20 to 25. Mu.L, more preferably 20. Mu.L; the ratio of the mass of the electrocatalyst material to the volume of the solvent is preferably from 5 to 6mg:1mL. The ratio of the mass of the electrocatalyst material to the volume of the solvent is 5-6 mg:1mL.
In one embodiment of the present invention, the controlled coating thickness in the step (4) is 0.5mm, and the drying is performed at 25 ℃.
The embodiment of the invention also provides the hexagonal boron nitride nanosheet-reduced graphene oxide composite material electrocatalyst prepared by any one of the preparation methods. The hexagonal boron nitride nanosheets-reduced graphene oxide composite material prepared by the embodiment of the invention is prepared by uniformly dispersing the hexagonal boron nitride nanosheets on a graphene plane, and the hexagonal boron nitride nanosheets and the reduced graphene oxide are formed into a plane heterostructure, are coupled by interlayer van der Waals acting force, have a large number of defect sites, do not contain additionally introduced functional groups, and do not contain any metal catalyst. In addition, the diameter of the hexagonal boron nitride nano-sheet is 1-10 μm, and the diameter of the reduced graphene oxide is 50-100 μm. The mass ratio of hexagonal boron nitride to reduced graphene oxide and the dispersity of hexagonal boron nitride on the surface of graphene in the composite material can be controlled by adjusting the ratio of the precursors of the boron nitride and the graphene in the step (2). Specifically, the mass ratio of the hexagonal boron nitride nano-sheets to the reduced graphene oxide is 1:1-1:7. In addition, the source of the graphene and hexagonal boron nitride precursors required in the preparation process of the composite material has no special requirement, and the hexagonal boron nitride nanosheets and the reduced graphene oxide which are commercially available or prepared by self in the field can be used.
The embodiment of the invention also provides the composite material electrocatalyst of any hexagonal boron nitride nanosheet-reduced graphene oxide and application of the composite material electrocatalyst in electrocatalytic oxygen evolution reaction. The composite electrocatalyst of the hexagonal boron nitride nanosheet-reduced graphene oxide, which is obtained by the invention, is used for the electrocatalytic oxygen evolution reaction, has the advantages of obviously improved catalytic efficiency, lower interface resistance, higher charge transfer efficiency and better stability compared with the reduced graphene oxide.
The invention will be described in detail with reference to examples.
Example 1
The preparation method of the hexagonal boron nitride-reduced graphene oxide composite material-based electrocatalyst comprises the following steps:
1. preparing hexagonal boron nitride nano-sheets:
(1) Weighing 1g of hexagonal boron nitride micro powder (particle size is 10 mu m) and 6g of potassium permanganate powder, and grinding to uniformly mix the powder;
(2) 120mL of concentrated sulfuric acid (with a mass concentration of 95%) and 15mL of phosphoric acid (with a mass concentration of 85%) are mixed to prepare a reaction solvent;
(3) 18mL of hydrogen peroxide (the mass concentration is 30%) and 120mL of deionized water are mixed, and the solution is frozen for 12h;
(4) Adding the mixed powder obtained in the step (1) into the mixed acid reaction solvent prepared in the step (2), magnetically stirring at 75 ℃ to enable the powder to fully react with acid, heating and stirring for 12 hours, adding the powder into ice cubes frozen by the hydrogen peroxide and deionized water mixed solution obtained in the step (3), continuously magnetically stirring under the ice water bath condition, and heating to room temperature after the reaction is fully carried out;
(5) Centrifuging the mixed solution obtained in the step (4) at 3000rpm for 15min, and removing the precipitate;
(6) Repeatedly washing the supernatant obtained in the step (5) with ethanol and deionized water alternately, and centrifuging at 18000rpm for 15min until the pH is >7 (about 3 times of repeated washing);
(7) And (3) drying the solution obtained in the step (6) in a vacuum drying oven at 45 ℃ for 24 hours to obtain the boron nitride nanosheets.
2. Preparation of graphene oxide:
(1) 1g of graphite micropowder (particle size 50 meshes) and 1g of sodium nitrate powder are weighed and uniformly mixed.
(2) 18mL of hydrogen peroxide (30% by mass) and 120mL of deionized water were mixed and the solution was incubated at 60℃for 1h.
(3) Slowly pouring 120mL of concentrated sulfuric acid (with the mass concentration of 95%) into the mixed powder obtained in the step (1); magnetic stirring was carried out at 5℃for 2h to allow the powder to react well with the acid.
(4) Weighing 6g of potassium permanganate, and slowly adding the potassium permanganate into the mixed solution obtained in the step (3). Continuously maintaining magnetic stirring at 5deg.C to allow the powder to react with acid, stirring for 2 hr, heating to 35deg.C, and stirring for 1 hr
(5) Centrifuging the mixed solution obtained in the step (4) at 3000rpm for 15min, and removing the precipitate;
(6) Repeatedly washing the supernatant obtained in the step (5) with ethanol and deionized water alternately, and centrifuging at 18000rpm for 15min until the pH is >7 (about 3 times of repeated washing);
(7) And (3) drying the solution obtained in the step (6) in a vacuum drying oven at 45 ℃ for 24 hours to obtain the boron nitride nanosheets.
3. Preparation of hexagonal boron nitride nanosheets-reduced graphene oxide composite materials:
(1) 20ml of graphene oxide dispersion liquid (with the concentration of 1 mg/ml) and 20mg of hexagonal boron nitride nanosheet powder are respectively measured, dispersed in 60ml of deionized water, stirred at the speed of 300r/min, and the stirred dispersion liquid is subjected to ultrasonic treatment with the ultrasonic power of 50W and the ultrasonic time of 15min, so that the dispersion liquid containing few layers of boron nitride nanosheets and graphene oxide is obtained.
(2) The dispersion is put into a reaction kettle with polytetrafluoroethylene with the capacity of 100ml as a lining, and is put into an oven for reaction, the temperature of the oven is set to 180 ℃, and the reaction time is 10 hours. And (3) putting the colloid after the reaction into a freeze dryer to dry to constant weight, wherein the freeze drying temperature is-50 ℃, and the freeze drying time is 10 hours, so that the hexagonal boron nitride nanosheet-reduced graphene oxide composite material is obtained.
Example 2
The preparation method of the hexagonal boron nitride-reduced graphene oxide composite material-based electrocatalyst is the same as that in example 1, and is different in that in the third step, 20ml (the concentration is 1 mg/ml) of graphene oxide dispersion liquid and 60mg of hexagonal boron nitride nanosheet powder are measured respectively.
Example 3
The preparation method of the hexagonal boron nitride-reduced graphene oxide composite material-based electrocatalyst is the same as that in example 1, and is different in that in the third step, 20ml (the concentration is 1 mg/ml) of graphene oxide dispersion liquid and 100mg of hexagonal boron nitride nanosheet powder are measured respectively.
Comparative example 1
The preparation method of the hexagonal boron nitride-reduced graphene oxide composite material-based electrocatalyst is the same as that in example 1, and is different in that in the third step, 20ml (1 concentration mg/ml) of graphene oxide dispersion liquid and 140mg of hexagonal boron nitride nanosheet powder are measured respectively. At this time, since the hexagonal boron nitride nanoplatelets are too high, clusters are generated and can no longer be uniformly distributed on the graphene plane, so that the obtained performance and the electrocatalytic effect are reduced.
Test example 1
Performance test of the hexagonal boron nitride-reduced graphene oxide composite electrocatalysts prepared in examples 1-3 and comparative example 1
X-ray photoelectron spectroscopy tests are respectively carried out on the reduced graphene oxide, the hexagonal boron nitride nano-sheet and the hexagonal boron nitride nano-sheet-reduced graphene oxide composite material, and the full spectrum is shown in figure 1. As can be seen from fig. 1, the composite material contains only B and N which are boron nitride and C which is graphite, and further, no other impurity peaks. In addition, the results of the X-ray photoelectron spectroscopy core electron spectra of the composite materials prepared in examples 1 to 3 are shown in FIGS. 2 to 4, wherein the B1s and N1s in the composite material prepared in example 2 are maximally shifted with respect to the standard spectrum position, so that the interlayer coupling charge transfer amount is maximized, and the electrocatalytic effect can be expected to be optimal. And the B-O bonding peak of B1s in the high energy direction in example 2 is most remarkable, indicating that a large amount of O-induced defects are generated during the preparation of the composite material.
The hexagonal boron nitride nanoplatelet-reduced graphene oxide composite material obtained in example 2 was further analyzed using a scanning electron microscope, and a photograph of the obtained scanning electron microscope is shown in fig. 5. As can be seen from fig. 5, the hexagonal boron nitride nanoplatelets are encapsulated by reduced graphene oxide. The obtained hexagonal boron nitride nanoplatelet-reduced graphene oxide composite material was analyzed using a transmission electron microscope, and the obtained transmission electron microscope image is shown in fig. 6. As can be seen from fig. 6, the hexagonal boron nitride nanoplatelets have significant point defects.
Test example 1
The effect of the hexagonal boron nitride nanosheet-reduced graphene oxide composite electrocatalyst prepared in example 2 and comparative example 1 on electrochemical oxygen evolution reaction was examined
Placing the hexagonal boron nitride nanosheets-reduced graphene oxide composite materials obtained in the example 2 and the comparative example 1 in an agate mortar, fully grinding, and then adding a solvent into the ground composite materials for ultrasonic dispersion to obtain pasty slurry; the solvent is a mixed solution of deionized water, teflon (Naflex) and isopropanol. Wherein 750 μl of deionized water, 250 μl of isopropanol, and 20 μl of Teflon; the mass of the electrocatalyst material was 5mg. And uniformly coating the obtained pasty slurry on the surface of foam nickel, controlling the coating thickness to be 0.5mm, and drying at 25 ℃ to obtain the electrocatalytic working electrode.
The electrocatalytic experiment test is carried out by using a three-port electrolytic cell, the prepared electrocatalytic working electrode, a mercury/mercury oxide reference electrode and a platinum sheet counter electrode form a three-electrode and two-loop test system, and 0.1mol/L potassium hydroxide solution is used as electrolyte. The catalytic performance of the oxygen reduction catalyst was measured using an electrochemical test system. As can be seen from the linear sweep voltammetric test chart of FIG. 7, the electrocatalyst catalytic activity of the composite material obtained in example 2 is significantly higher than that of the reduced graphene oxide and hexagonal boron nitride nanoplatelets, and has a potential of 6.4mA cm at 1.6V electrode -2 Is at 10mA cm -2 Has an overpotential of 1.65V lower. FIG. 8 Tafil plot shows that the hexagonal boron nitride nanosheet-reduced graphene oxide composite electrocatalyst has a comparable reduced graphene oxide 314mV dec -1 And hexagonal boron nitride nanoplate 789mV dec -1 Lower tafel slope 279 mddec -1 . As can be seen from the electrochemical impedance diagram of fig. 9, the hexagonal boron nitride nano-sheet-reduced graphene oxide composite electrocatalyst has lower interface resistance and higher charge transfer efficiency than reduced graphene oxide. From the stability test of fig. 10, it can be known that the hexagonal boron nitride nano-sheet-reduced graphene oxide composite electrocatalyst can stably work for 20000s, and has more excellent stability compared with reduced graphene oxide.
The composite electrocatalyst of comparative example 1 has poor catalytic effect, mainly because the mass ratio of boron nitride is too high, and the boron nitride cannot be uniformly dispersed on the graphene sheets to generate clusters.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (4)
1. The electro-catalyst based on the hexagonal boron nitride nanosheets-reduced graphene oxide composite material is characterized in that the electro-catalyst is a hexagonal boron nitride nanosheets-reduced graphene oxide interlayer composite material, the diameter of the hexagonal boron nitride nanosheets is 1-10 mu m, the hexagonal boron nitride nanosheets are uniformly dispersed on a graphene plane, the diameter of the reduced graphene oxide is 50-100 mu m, the hexagonal boron nitride nanosheets and the reduced graphene oxide are in a plane heterostructure, interlayer van der Waals acting force coupling is achieved, the composite material has a large number of O-related defect sites, B-O bonds are formed, no additional introduced functional groups are contained, and no metal catalyst is contained;
the hexagonal boron nitride nanosheets and the reduced graphene oxide are compounded by adopting a hydrothermal synthesis method and a freeze drying mode; setting the temperature of an oven of the hydrothermal synthesis method to 180 ℃ and the reaction time to 10 hours;
the composite material electrocatalyst is characterized in that the mass ratio of the reduced graphene oxide to the hexagonal boron nitride nanosheets can be 1:1-1:7.
2. The preparation method of the hexagonal boron nitride nanosheet-reduced graphene oxide composite material-based electrocatalyst according to claim 1, comprising the following steps:
ultrasonically dispersing the electrochemical catalyst in a solvent to obtain pasty slurry;
and coating the pasty slurry on the surface of an electrochemical electrode element and drying to obtain the hexagonal boron nitride nanosheet-reduced graphene oxide composite material-based electrochemical catalyst.
3. The preparation method according to claim 2, wherein the ratio of the mass of the electrocatalyst material to the volume of the solvent in step (1) is 5 to 6mg:1mL.
4. The application of the hexagonal boron nitride nano-sheet-reduced graphene oxide composite material-based electrocatalyst prepared by the preparation method according to any one of claims 2 to 3 in electrocatalytic oxygen reduction.
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