CN114427103A - Electrocatalyst based on hexagonal boron nitride nanosheet-reduced graphene oxide composite material and preparation method and application thereof - Google Patents
Electrocatalyst based on hexagonal boron nitride nanosheet-reduced graphene oxide composite material and preparation method and application thereof Download PDFInfo
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- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
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- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
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- 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
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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
- 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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Abstract
The invention provides a hexagonal boron nitride nanosheet-reduced graphene oxide composite material-based electrocatalyst and a preparation method and application thereof, and belongs to the technical field of new materials. 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, the overpotential of the reaction is effectively reduced through the coupling effect of the defect sites between the hexagonal boron nitride nanosheet and the reduced graphene oxide layer, the electrocatalytic efficiency is improved, the stability is good, and the hexagonal boron nitride nanosheet-reduced graphene oxide composite material can be used as a metal-free catalyst to be applied to the electrocatalytic oxidation-reduction reaction.
Description
Technical Field
The invention relates to the technical field of new materials, and particularly relates to an electrocatalyst based on a hexagonal boron nitride nanosheet-reduced graphene oxide composite material, and a preparation method and application thereof.
Background
The hydrogen energy is a recognized clean energy in the world at present, the hydrogen is mainly obtained by using electrolytic water as a main mode at present, and the electrolytic water reaction mainly comprises a cathodic hydrogen evolution reaction (HER reaction) and an anodic oxygen evolution reaction (OER reaction). The oxygen evolution reaction consists of a four-electron transfer process, and the overpotential is high in the reaction, the material circulation stability is poor, the efficiency of electrocatalytic oxygen evolution is limited, and the development of an efficient and stable oxygen evolution reaction electrocatalyst is urgently needed.
At present, although the activity of noble metal oxygen evolution reaction catalysts represented by iridium oxide and ruthenium oxide is high, 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 maintaining good catalytic effect, it has become a research hotspot to find other high-performance and cheap catalytic materials by partially or completely replacing precious metals. In view of the cost, source and convenience of practical application of the catalytic material, carbon-based catalytic materials tend to be cheap and have high thermal stability. In particular, the discovery of two-dimensional materials such as graphene, boron nitride, molybdenum disulfide, and the like has focused on two-dimensional layered materials at the atomic level. The graphene and the boron nitride are used as outstanding representatives in two-dimensional materials, have the advantages of large specific surface area, more active sites, simple synthesis process and the like, and become an ideal catalyst to be applied to hydrogen production by electrolyzing water. In actual operation, however, graphene has a zero band gap structure and high conductivity, but the stability in chemical catalytic reaction is poor; hexagonal boron nitride has extremely excellent chemical stability and thermal stability, but due to the ultra-wide band gap, electrical insulation is also a main factor for preventing the hexagonal boron nitride from being used in electrocatalytic reaction. Therefore, enabling the composite material of hexagonal boron nitride and graphene to develop new properties without a metal catalyst is a completely new challenge.
At present, there are also reports in the literature that a hexagonal boron nitride/graphene composite material is prepared by a hydrothermal method, and a nitride precursor and graphene oxide are mainly mixed and then subjected to a hydrothermal synthesis reaction to finally form the hexagonal boron nitride/reduced graphene oxide composite material. However, the hexagonal boron nitride/reduced graphene oxide composite material formed by the method is not pure enough and low in quality, and a large number of precursors which are not completely reacted exist, so that the catalytic efficiency is low. In conclusion, the hexagonal boron nitride-reduced graphene oxide composite material electrocatalyst prepared by the invention has the advantages that the respective characteristics are considered, the respective weaknesses are overcome and improved, and the electrocatalytic performance is further improved.
Disclosure of Invention
In view of the above, the invention aims to provide an electrocatalyst based on a hexagonal boron nitride nanosheet-reduced graphene oxide composite material, 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 is low in cost and good in catalytic performance. And the preparation method is simple and is beneficial to industrial 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, wherein the catalyst material is a hexagonal boron nitride nanosheet-reduced graphene oxide, and is characterized in that the hexagonal boron nitride nanosheet is 1-10 microns in diameter and is uniformly dispersed on a graphene plane; the diameter of the reduced graphene oxide is 50-100 microns, the hexagonal boron nitride nanosheet and the reduced graphene oxide are of planar heterostructure and are coupled by an interlayer van der Waals acting force, and the composite material has a large number of defect sites, does not contain an additionally introduced functional group and does not contain any metal catalyst; the mass ratio of the graphene oxide to the hexagonal boron nitride nanosheet 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) 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 carrying out ultrasonic treatment on the stirred dispersion liquid to obtain the dispersion liquid containing few-layer boron nitride nanosheets and graphene oxide.
(2) And (3) putting the dispersion liquid into a reaction kettle with polytetrafluoroethylene as a lining, and putting the reaction kettle into an oven for reaction. And putting the reacted colloid into a freeze dryer to dry to constant weight, thus obtaining the hexagonal boron nitride nanosheet-reduced graphene oxide composite material.
(3) Ultrasonically dispersing the electrocatalyst in a solvent to obtain pasty slurry;
(4) the paste slurry is applied to the surface of an electrocatalytic electrode element and dried, and an electrocatalytic electrode can be performed.
Preferably, the solvent in step (3) is a mixed solution of teflon (nafion) and isopropanol.
Preferably, the ratio of the mass of the electrocatalyst material to the volume of the solvent in the step (3) is 5-6 mg: 1 mL.
The invention also provides an application of the electrocatalyst based on the hexagonal boron nitride nanosheet-reduced graphene oxide composite material in electrocatalytic oxidation reduction.
The invention has the beneficial effects that:
1. the invention provides a hexagonal boron nitride nanosheet-reduced graphene oxide composite material which is prepared from hexagonal boron nitride nanosheets and graphene oxide as raw materials in a hydrothermal synthesis mode, wherein the hexagonal boron nitride nanosheets are uniformly distributed on the surface of a graphene thin layer, and the hexagonal boron nitride nanosheets and the graphene are easily combined, so that defect sites are obvious, and the lamellar distribution is uniform, and the improvement of the performance of the catalyst is facilitated.
2. The composite material based on hexagonal boron nitride nanosheet-reduced graphene oxide has more defect active sites and good conductivity, and in addition, the catalytic performance of the composite material is further improved and the electron transfer resistance is reduced through the strong coupling effect of the double-layer defect sites, so that the prepared catalytic material has high oxygen evolution activity and stability.
3. The invention provides a 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 incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a full spectrum of X-ray photoelectron spectra of hexagonal boron nitride nanosheet-graphene oxide composites, hexagonal boron nitride nanosheets and reduced graphene oxide prepared in examples 1-3 and comparative example 1;
FIG. 2 is an X-ray photoelectron spectroscopy core electron spectroscopy spectrum of the hexagonal boron nitride nanosheet-reduced graphene oxide composite prepared in example 1;
FIG. 3 is an X-ray photoelectron spectroscopy core electron spectroscopy spectrum of the hexagonal boron nitride nanosheet-reduced graphene oxide composite prepared in example 2;
FIG. 4 is an X-ray photoelectron spectroscopy core electron spectroscopy spectrum of the hexagonal boron nitride nanosheet-reduced graphene oxide composite prepared in example 3;
FIG. 5 is a scanning electron microscope image (a: low magnification; b: high magnification) of the hexagonal boron nitride nanosheet-reduced graphene oxide composite prepared in example 2;
fig. 6 is a transmission electron microscope image of the hexagonal boron nitride nanosheet-reduced graphene oxide composite prepared in example 2;
FIG. 7 is an electrochemical linear scanning voltammogram of the hexagonal boron nitride nanosheet-graphene oxide composite material, the hexagonal boron nitride nanosheet, and the reduced graphene oxide obtained in example 2;
FIG. 8 is a graph of electrochemical Tafel slopes of the hexagonal boron nitride nanosheet-graphene oxide composite, the hexagonal boron nitride nanosheets, and the reduced graphene oxide obtained in example 2;
FIG. 9 is an electrochemical AC impedance plot of the hexagonal boron nitride nanosheet-graphene oxide composite, the hexagonal boron nitride nanosheets, and the reduced graphene oxide obtained in example 2;
fig. 10 is a graph comparing electrochemical stability of the hexagonal boron nitride nanosheet-graphene oxide composite obtained in example 2 with that of reduced graphene oxide.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
The invention provides a preparation method of an electrocatalyst based on a hexagonal boron nitride nanosheet-reduced graphene oxide composite material, which comprises the following steps:
(1) 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 carrying out ultrasonic treatment on the stirred dispersion liquid to obtain the dispersion liquid containing few-layer boron nitride nanosheets and graphene oxide.
(2) And (3) putting the dispersion liquid into a reaction kettle with polytetrafluoroethylene as a lining, and putting the reaction kettle into an oven for reaction. And putting the reacted colloid into a freeze dryer to dry to constant weight, thus 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 the foamed nickel and drying to obtain the electrocatalytic working electrode.
In an embodiment of the invention, the mass ratio of the reduced graphene oxide to the hexagonal boron nitride in the step (1) may be controlled to be 1:1-1:7, and specifically may be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, and the like.
In an embodiment of the present invention, the solvent in the step (3) is a mixed solution of deionized water, teflon (nafion) and isopropanol, and a solvent volume ratio of the deionized water to the isopropanol is preferably 500 to 750 μ L: 250 μ L, more preferably 750 μ L: 250 mu L; the volume of the teflon solvent is preferably 20-25 mu L, and more preferably 20 mu L; the preferred ratio of the mass of the electrocatalyst material to the volume of the solvent is 5-6 mg: 1 mL. The ratio of the mass of the electrocatalyst material to the volume of the solvent is 5-6 mg: 1 mL.
In one embodiment of the present invention, the coating thickness in the step (4) is controlled to be 0.5mm, and the drying is performed at 25 ℃.
An embodiment of the invention further provides the hexagonal boron nitride nanosheet-reduced graphene oxide composite material electrocatalyst prepared by any one of the preparation methods. The hexagonal boron nitride nanosheet-reduced graphene oxide composite material prepared by the embodiment of the invention is formed by uniformly dispersing the hexagonal boron nitride nanosheets on a graphene plane, so that the hexagonal boron nitride nanosheets and the reduced graphene oxide are of planar heterostructure, are coupled by an 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 nanosheet is 1-10 μm, and the diameter of the reduced graphene oxide is 50-100 μm. By adjusting the ratio of the boron nitride to the graphene precursor in the step (2), the mass ratio of the hexagonal boron nitride to the reduced graphene oxide in the composite material and the dispersity of the hexagonal boron nitride on the surface of the graphene can be controlled. Specifically, the mass ratio of the hexagonal boron nitride nanosheet to the reduced graphene oxide is 1:1-1: 7. In addition, the graphene and hexagonal boron nitride precursor sources required in the preparation process of the composite material have no special requirements, and the hexagonal boron nitride nanosheets and the reduced graphene oxide which are conventionally sold or prepared by self in the field can be used.
An embodiment of the invention also provides the composite material electrocatalyst of any one hexagonal boron nitride nanosheet-reduced graphene oxide and application thereof in electrocatalytic oxygen evolution reaction. The composite material electrocatalyst of hexagonal boron nitride nanosheet-reduced graphene oxide obtained by the invention is used for electrocatalytic oxygen evolution reaction, the catalytic efficiency is obviously improved, the interface resistance is lower, the charge transfer efficiency is higher, and the stability is more excellent than that of the reduced graphene oxide.
The present invention will be described in detail with reference to examples.
Example 1
A preparation method of an electrocatalyst based on a hexagonal boron nitride-reduced graphene oxide composite material comprises the following steps:
firstly, preparing hexagonal boron nitride nanosheets:
(1) weighing 1g of hexagonal boron nitride micro powder (with the particle size of 10 mu m) and 6g of potassium permanganate powder, and grinding to uniformly mix the hexagonal boron nitride micro powder and the potassium permanganate powder;
(2) mixing 120mL of concentrated sulfuric acid (with the mass concentration of 95%) and 15mL of phosphoric acid (with the mass concentration of 85%) to serve as a reaction solvent;
(3) mixing 18mL (mass concentration is 30%) of hydrogen peroxide with 120mL of deionized water, and freezing the solution for 12 h;
(4) adding the mixed powder obtained in the step (1) into the mixed acid reaction solvent prepared in the step (2), performing magnetic stirring at 75 ℃ to ensure that the powder and the acid fully react, heating and stirring for 12 hours, adding the powder into ice blocks frozen by the mixed solution of hydrogen peroxide and deionized water in the step (3), continuing the magnetic stirring under the condition of ice-water bath, and heating to room temperature after full reaction;
(5) centrifuging the mixed solution obtained in the step (4) at 3000rpm for 15min, and removing precipitates;
(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 greater than 7 (washing is repeated for about 3 times);
(7) and (5) drying the solution obtained in the step (6) in a vacuum drying oven at 45 ℃ for 24 hours to obtain the boron nitride nanosheet.
Secondly, preparing graphene oxide:
(1) weighing 1g of graphite micropowder (with the particle size of 50 meshes) and 1g of sodium nitrate powder, and uniformly mixing.
(2) 18mL (30% by mass) of hydrogen peroxide and 120mL of deionized water are mixed, and the solution is incubated at 60 ℃ for 1 h.
(3) Slowly pouring 120mL of concentrated sulfuric acid (the mass concentration is 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) 6g of potassium permanganate is weighed and slowly added into the mixed solution obtained in the step (3). Continuously keeping the temperature at 5 ℃ and stirring magnetically to enable the powder to react with the acid fully, stirring for 2h, raising the temperature to 35 ℃, heating and stirring for 1h
(5) Centrifuging the mixed solution obtained in the step (4) at 3000rpm for 15min, and removing precipitates;
(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 greater than 7 (washing is repeated for about 3 times);
(7) and (4) drying the solution obtained in the step (6) in a vacuum drying oven at 45 ℃ for 24 hours to obtain the boron nitride nanosheet.
Thirdly, preparing the hexagonal boron nitride nanosheet-reduced graphene oxide composite material:
(1) respectively measuring 20ml (with the concentration of 1mg/ml) of graphene oxide dispersion liquid and 20mg of hexagonal boron nitride nanosheet powder, dispersing the graphene oxide dispersion liquid and the hexagonal boron nitride nanosheet powder in 60ml of deionized water, stirring at the speed of 300r/min, and carrying out ultrasonic treatment on the stirred dispersion liquid, wherein the ultrasonic power is 50W, and the ultrasonic time is 15min, so as to obtain the dispersion liquid containing the few-layer boron nitride nanosheets and the graphene oxide.
(2) And (3) filling the dispersion into a reaction kettle with 100ml of polytetrafluoroethylene as a lining, and putting the reaction kettle into an oven for reaction, wherein the temperature of the oven is set to be 180 ℃, and the reaction time is 10 hours. And putting the reacted colloid 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 as to obtain the hexagonal boron nitride nanosheet-reduced graphene oxide composite material.
Example 2
The preparation method of the electrocatalyst based on the hexagonal boron nitride-reduced graphene oxide composite material is the same as that in example 1, except that in the third step, 20ml of graphene oxide dispersion liquid (with the concentration of 1mg/ml) and 60mg of hexagonal boron nitride nanosheet powder are respectively measured.
Example 3
The preparation method of the electrocatalyst based on the hexagonal boron nitride-reduced graphene oxide composite material is the same as that in example 1, except that in the third step, 20ml (with a concentration of 1mg/ml) of the graphene oxide dispersion liquid and 100mg of the hexagonal boron nitride nanosheet powder are respectively measured.
Comparative example 1
The preparation method of the electrocatalyst based on the hexagonal boron nitride-reduced graphene oxide composite material is the same as that in example 1, except that in the third step, 20ml (1 mg/ml) of graphene oxide dispersion liquid and 140mg of hexagonal boron nitride nanosheet powder are respectively measured. At this time, the hexagonal boron nitride nanosheets 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 both reduced.
Test example 1
Performance testing of hexagonal boron nitride-reduced graphene oxide composite electrocatalysts prepared in examples 1-3 and comparative example 1
The reduced graphene oxide, the hexagonal boron nitride nanosheet and the hexagonal boron nitride nanosheet-reduced graphene oxide composite material are subjected to X-ray photoelectron spectroscopy test respectively, and the full spectrum of the X-ray photoelectron spectroscopy test is shown in figure 1. As can be seen from fig. 1, only B and N belonging to boron nitride and C belonging to graphite were contained in the composite material, and no other impurity peak was observed. In addition, the X-ray photoelectron spectroscopy core electron spectroscopy results of the composite materials prepared in examples 1 to 3 are shown in fig. 2 to 4, in which B1s and N1s are most shifted from the standard spectral position in the composite material prepared in example 2, and thus the interlayer coupling charge transfer amount is the largest, and the electrocatalytic effect can be expected to be the best. And the B — O bonding peak of B1s in the high energy direction is most pronounced in example 2, indicating that a large number of O-induced defects are generated during the preparation of the composite material.
The hexagonal boron nitride nanosheet-reduced graphene oxide composite material obtained in example 2 was further analyzed using a scanning electron microscope, and the obtained scanning electron microscope photograph is shown in fig. 5. As can be seen from fig. 5, the hexagonal boron nitride nanosheets are encapsulated by the reduced graphene oxide. The obtained hexagonal boron nitride nanosheet-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 nanosheets have significant point defects.
Test example 1
Investigating the effect of the hexagonal boron nitride nanosheet-reduced graphene oxide composite electrocatalyst prepared in example 2 and comparative example 1 on the electrochemical oxygen evolution reaction
Placing the hexagonal boron nitride nanosheet-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 (Naflion) and isopropanol. Wherein, 750 mu L of deionized water, 250 mu L of isopropanol and 20 mu L of teflon are added; the mass of the electrocatalyst material was 5 mg. And uniformly coating the obtained pasty slurry on the surface of the foamed nickel, controlling the coating thickness to be 0.5mm, and drying at 25 ℃ to obtain the electrocatalytic working electrode.
And (3) carrying out an electrocatalysis experiment test by using a three-port electrolytic cell, forming a three-electrode and two-loop test system by using the prepared electrocatalysis working electrode, a mercury/mercury oxide reference electrode and a platinum sheet counter electrode, and using 0.1mol/L potassium hydroxide solution as electrolyte. And measuring the catalytic performance of the oxygen reduction reaction catalyst by using an electrochemical test system. As shown in a linear scanning voltammetry test chart of FIG. 7, the electrocatalyst catalytic activity of the composite material obtained in example 2 is significantly higher than that of reduced graphene oxide and hexagonal boron nitride nanosheets, and has a concentration of 6.4mA cm/cm under an electrode potential of 1.6V-2Current density of (2) at 10mA cm-2Has a lower overpotential of 1.65V at the current density of (2). As can be seen from the Tafel plot of FIG. 8, the hexagonal boron nitride nanosheet-reduced graphene oxide composite electrocatalyst has a reduced graphene oxide 314mV dec-1And hexagonal boron nitride nanosheet 789mV dec-1Lower Tafel slope 279mVdec-1. As can be seen from the electrochemical impedance diagram of fig. 9, the hexagonal boron nitride nanosheet-reduced graphene oxide composite electrocatalyst has lower interfacial resistance and higher charge transfer efficiency than the reduced graphene oxide and the hexagonal boron nitride nanosheets. As can be seen from the stability test in fig. 10, the hexagonal boron nitride nanosheet-reduced graphene oxide composite electrocatalyst can stably work for 20000s, and has more excellent stability than the reduced graphene oxide.
The composite material electrocatalyst of comparative example 1 has a 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 sheet layer to generate clusters.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The electrocatalyst based on the hexagonal boron nitride nanosheet-reduced graphene oxide composite material is characterized in that the electrochemical catalyst is the hexagonal boron nitride nanosheet-reduced graphene oxide interlayer composite material, the diameter of the hexagonal boron nitride nanosheet is 1-10 microns, the hexagonal boron nitride nanosheet is uniformly dispersed on a graphene plane, the diameter of the reduced graphene oxide is 50-100 microns, the hexagonal boron nitride nanosheet and the reduced graphene oxide are of planar heterostructure and are coupled by van der Waals acting force between layers, the composite material has a large number of defect sites, does not contain additionally introduced functional groups, and does not contain any metal catalyst.
2. The hexagonal boron nitride nanosheet-reduced graphene oxide composite-based electrocatalyst according to claim 1, wherein the hexagonal boron nitride nanosheets are composited with reduced graphene oxide using a hydrothermal synthesis method and a freeze-drying manner.
3. The hexagonal boron nitride nanosheet-reduced graphene oxide composite electrocatalyst based on claim 1, wherein the mass ratio of reduced graphene oxide to hexagonal boron nitride nanosheets may be from 1:1 to 1: 7.
4. The preparation method of the hexagonal boron nitride nanosheet-reduced graphene oxide composite electrocatalyst based on any one of claims 1 to 3, comprising the steps of:
(1) ultrasonically dispersing the electrochemical catalyst in a solvent to obtain pasty slurry;
(2) and coating the pasty slurry on the surface of an electrochemical electrode element and drying to obtain the electrochemical catalyst based on the hexagonal boron nitride nanosheet-reduced graphene oxide composite material.
5. The preparation method according to claim 4, wherein the solvent volume ratio of the deionized water to the isopropanol in the step (1) is preferably 500-750 μ L: 250 μ L, more preferably 750 μ L: 250 mu L; the volume of the teflon solvent is preferably 20-25 mu L, and more preferably 20 mu L; the preferred ratio of the mass of the electrocatalyst material to the volume of the solvent is 5-6 mg: 1 mL.
6. The preparation method according to claim 4, wherein the ratio of the mass of the electrocatalyst material to the volume of the solvent in step (1) is 5 to 6 mg: 1 mL.
7. Use of the hexagonal boron nitride nanosheet-reduced graphene oxide composite-based electrocatalyst according to any one of claims 1 to 3 or the hexagonal boron nitride nanosheet-reduced graphene oxide composite-based electrocatalyst prepared according to the preparation method of any one of claims 4 to 6 in electrocatalytic oxygen reduction.
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