CN113846341B - Preparation method and preparation device of black phosphorus-graphene heterojunction loaded nickel nitride - Google Patents
Preparation method and preparation device of black phosphorus-graphene heterojunction loaded nickel nitride Download PDFInfo
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Abstract
The invention relates to the technical field of new materials, and discloses a preparation method of black phosphorus-graphene heterojunction loaded nickel nitride, which comprises the following steps: s1) respectively weighing red phosphorus powder and cellulose powder, dispersing in deionized water, and performing ultrasonic treatment to obtain a dispersion liquid containing a combination of red phosphorus and cellulose; s2) adding nickel nitride particles into the dispersion liquid, stirring, and putting the stirred mixed solution into a vacuum oven to dry to constant weight to obtain a mixture; s3) putting the mixture into a high-voltage discharge cavity, and performing high-voltage discharge processing to obtain a crude product; s4) dispersing the crude product in absolute ethyl alcohol, injecting the absolute ethyl alcohol into a centrifuge tube, then placing the centrifuge tube into a centrifuge for centrifugal purification to obtain a refined product, placing the refined product into a vacuum oven for drying until the weight is constant, and thus obtaining the black phosphorus-graphene heterojunction loaded nickel nitride, wherein the prepared product has high quality and low cost; the device for implementing the preparation method of the black phosphorus-graphene heterojunction loaded nickel nitride is also provided, and the production efficiency is high.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a preparation method and a preparation device of black phosphorus-graphene heterojunction loaded nickel nitride.
Background
Hydrogen energy is a recognized clean energy, and the current hydrogen production mode mainly adopts electrolytic water, and the electrolytic water reaction mainly comprises a cathode hydrogen evolution reaction (HER reaction) and an anode oxygen evolution reaction (OER reaction).
Since the OER reaction is a four-electron transfer process, its overpotential is high and kinetics is slow, limiting hydrogen evolution efficiency, and there is a need to develop an efficient and durable oxygen evolution reaction electrocatalyst in the electrolytic water reaction.
The existing OER oxygen evolution reaction electrocatalysts represented by ruthenium-based and iridium-based catalysts are expensive.
Inspired by graphene, people are trying to search other two-dimensional layered materials with atomic layer thickness, and recently, a black phosphorus-graphene heterojunction nickel nitride nanoparticle-loaded material is paid attention to and is applied to an OER oxygen evolution electrocatalytic reaction.
The preparation method of the black phosphorus-graphene in the prior art comprises the following steps: mechanical stripping methods and liquid phase stripping methods.
The mechanical stripping method needs to ball-mill for more than 40 hours by using a ball mill under the protection of inert gas, has low production efficiency, is difficult to control the size and the thickness of a layer, reduces the electrochemical performance of the material and limits the application of the material.
The liquid phase stripping method has high yield, but the product has small size, and a large amount of organic solvent is needed in the production process, so that the organic solvent is difficult to remove in the later period, and the method does not accord with the environmental protection concept.
Disclosure of Invention
Based on the existing technical defects, the invention provides the preparation method of the black phosphorus-graphene heterojunction loaded nickel nitride, which has the characteristics of simple process and high efficiency, and solves the technical problems of high cost, low production efficiency and environmental pollution of the preparation method of the black phosphorus-graphene in the prior art.
The invention also aims to provide a preparation device for producing the black phosphorus-graphene heterojunction loaded nickel nitride, which is simple in structure, can realize rapid and large-batch preparation of the black phosphorus-graphene heterojunction loaded nickel nitride and has very high production efficiency.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of black phosphorus-graphene heterojunction loaded nickel nitride comprises the following steps:
s1) respectively weighing red phosphorus powder and cellulose powder, dispersing in deionized water, and performing ultrasonic treatment to obtain a dispersion liquid containing a red phosphorus-cellulose combination;
s2) adding nickel nitride particles into the dispersion liquid to form a mixed solution, stirring, and putting the stirred mixed solution into a vacuum oven to dry to constant weight to obtain a mixture;
s3) putting the mixture into a high-voltage discharge cavity, and performing high-voltage discharge processing to obtain a crude product;
s4) dispersing the crude product in absolute ethyl alcohol, injecting the absolute ethyl alcohol into a centrifugal tube, placing the centrifugal tube into a centrifuge for centrifugal purification to form a refined product, and then placing the refined product after purification into a vacuum oven to dry to constant weight, so that the black phosphorus-graphene heterojunction loaded nickel nitride is prepared.
Specifically, in step S1), the mass ratio of the red phosphorus powder to the cellulose powder is 1: 1.
preferably, in step S1), the ultrasonic treatment time is 5-10min, and the mass concentration of the red phosphorus-cellulose combination in the dispersion liquid is 2-10 mg/ml.
Preferably, in step S2), the mass ratio of the nickel nitride particles to the red phosphorus-cellulose conjugate is 1: (2-10).
5. The method as claimed in claim 1, wherein in step S2), the rotation speed of stirring is 300-500r/min, and the drying temperature is 50-70 ℃.
Further, in step S3), a quartz filler tube is installed in the high-voltage discharge chamber, and the quartz filler tube is used for placing the mixture;
the air pressure in the high-voltage discharge cavity is 5-8GPa, the discharge voltage is 300-400V, the discharge capacitance is 270-360mF, the discharge time is less than 2 seconds, and if the discharge time is too long and exceeds 2 seconds, the re-discharge operation is carried out until the time from the beginning to the end of single discharge does not exceed 2 seconds.
Preferably, in the step S4), the mass concentration of the crude product in the absolute ethyl alcohol is 2-10 mg/ml;
the rotating speed of the centrifuge is 500-700r/min, and the drying temperature is 50-70 ℃.
Furthermore, the invention also provides a preparation device for producing the black phosphorus-graphene heterojunction loaded nickel nitride, which is used for implementing the preparation method for the black phosphorus-graphene heterojunction loaded nickel nitride, and comprises a controller group, a high-voltage charging power supply group and the high-voltage discharge cavity;
the high-voltage charging power supply group comprises a silicon controlled rectifier component, a high-voltage charging power supply and a capacitor group;
a quartz filler tube is arranged in the high-voltage discharge cavity and used for placing the mixture;
high-voltage discharge electrodes are arranged at two ends of the quartz filler tube, and the two high-voltage discharge electrodes are respectively and electrically connected with positive and negative electrodes of the high-voltage charging power supply pack;
the controller group with high voltage charging power supply package electric connection, the controller group is equipped with long-range infrared controller.
Furthermore, the inner wall of the quartz filler tube is provided with a high-temperature resistant coating, and the temperature resistance value of the high-temperature resistant coating is greater than 3000K.
Further, the high-voltage discharge cavity is also connected with an inflator pump;
the capacitor bank is formed by combining a plurality of groups of 18mF capacitors; when the capacitor bank is charged, the connection between the high-voltage charging power supply bank and the high-voltage discharging electrode is cut off through the controller bank.
The technical scheme of the invention has the beneficial effects that: the preparation method of the black phosphorus-graphene heterojunction loaded nickel nitride comprises the steps of taking red phosphorus and cellulose as raw materials, preparing a carrier of a heterojunction formed by the black phosphorus and the graphene, then loading nickel nitride particles, and uniformly distributing the nickel nitride particles on a lamellar heterojunction substrate formed by the black phosphorus and the graphene, wherein the nickel nitride particles are used as an electrocatalyst of an OER oxygen evolution reaction and have good electrocatalytic activity in an alkaline environment.
The method specifically comprises the following advantages:
1. the cellulose is used as a carbon source, so that the cost of raw materials for preparing graphene is effectively reduced.
2. The black phosphorus is prepared from red phosphorus which is an allotrope of black phosphorus, and a heating source is provided for the high-temperature and high-pressure environment required by the discharge processing process by utilizing the combustion characteristic of the red phosphorus under the high-temperature condition.
3. The high-voltage discharge cavity in the device can provide high pressure of more than 10GPa, and can provide favorable high-voltage environment for the generation of black phosphorus and graphene.
4. The instantaneous high-voltage discharge can enable the temperature in the high-voltage discharge cavity to reach 3000K instantly, so that raw materials react instantly to form a two-dimensional lamellar structure, and impurities are purified instantly; graphene and black phosphorus form a stable heterojunction through transient discharge machining, graphene and black phosphorus generate turbo-stack-like lamellar graphene and lamellar black phosphorus in discharge, sp2 hybridized covalent bonds contained in the graphene and black phosphorus are recombined, and nickel nitride particles are loaded in the heterojunction.
5. Graphene and black phosphorus are two-dimensional materials with very large specific surface areas, van der waals force widely exists between sheet layers, and the conventional technology cannot completely overcome the van der waals force, so that the agglomeration phenomenon of the graphene and the black phosphorus cannot be effectively solved; by using the preparation method of the high-voltage discharge processing, in the high-voltage discharge process, charges move along the two-dimensional network of the graphene and the black phosphorus, a great coulomb force impact force is generated instantly, the coulomb force overcomes the van der Waals force effect causing agglomeration, and the agglomeration of the graphene and the black phosphorus is prevented.
6. The preparation method and the preparation device for the electric discharge machining have high production efficiency and short discharge time, so that large batches of products can be prepared in a short production period.
7. And by adopting the discharge machining process, toxic reagents can be avoided, and the method is more environment-friendly.
Drawings
FIG. 1 is a schematic structural diagram of an embodiment of a preparation device for producing black phosphorus-graphene heterojunction loaded nickel nitride according to the invention;
wherein: a controller group 1; a high-voltage charging power pack 2; a silicon controlled rectifier component 21; a high-voltage charging power supply 22; a capacitor bank 23; a high-voltage discharge chamber 3; a high-voltage discharge electrode 31; a quartz filler tube 32 and an inflator 4.
Detailed Description
In the description herein, references to the description of the terms "embodiment," "example," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
The technical solution of the present invention will be further described with reference to the following embodiments.
A preparation method of black phosphorus-graphene heterojunction loaded nickel nitride comprises the following steps:
s1) respectively weighing red phosphorus powder and cellulose powder, dispersing in deionized water, and performing ultrasonic treatment to obtain a dispersion liquid containing a red phosphorus-cellulose combination;
s2) adding nickel nitride particles into the dispersion liquid to form a mixed solution, stirring, and putting the stirred mixed solution into a vacuum oven to dry to constant weight to obtain a mixture;
s3) putting the mixture into a high-voltage discharge cavity 3, and performing high-voltage discharge machining to obtain a crude product;
s4) dispersing the crude product in absolute ethyl alcohol, injecting the absolute ethyl alcohol into a centrifugal tube, placing the centrifugal tube into a centrifuge for centrifugal purification to form a refined product, and then placing the refined product after purification into a vacuum oven to dry to constant weight, so that the black phosphorus-graphene heterojunction loaded nickel nitride is prepared.
The preparation method of the black phosphorus-graphene heterojunction loaded nickel nitride comprises the steps of taking red phosphorus and cellulose as raw materials, preparing a carrier of a heterojunction formed by the black phosphorus and the graphene, then loading nickel nitride particles, and uniformly distributing the nickel nitride particles on a lamellar heterojunction substrate formed by the black phosphorus and the graphene, wherein the nickel nitride particles are used as an electrocatalyst of an OER oxygen evolution reaction and have good electrocatalytic activity in an alkaline environment.
The invention implements accurate discharge processing aiming at the formula material, in the discharge process, the raw material is converted into graphene and black phosphorus in millisecond-level time unit, and a heterojunction is formed, and meanwhile, nickel nitride particles are also loaded on a lamellar structure of the heterojunction, so that the method has the characteristics of high efficiency, low cost and high stability, and the method is simple in process and free of secondary pollution.
During the discharge process, the substances in the high-voltage discharge cavity change as follows:
1. during the discharging process, the generated joule heat raises the temperature in the quartz filler tube to about 200 ℃, the red phosphorus starts to be violently combusted, the temperature continues to rise, the cellulose in the quartz filler tube is rapidly carbonized when the temperature reaches 280 ℃, and the temperature in the high-voltage discharge cavity is further raised.
2. In the discharging process, when the generated joule heat is further increased, the temperature in the quartz filler tube is raised to about 3000K, impurities in the tube are instantly sublimated, carbonized cellulose and red phosphorus are instantly and rapidly converted into graphene and black phosphorus, a heterojunction is formed, meanwhile, charges move along a two-dimensional network of a heterojunction material, and extremely large impact force (coulomb force) is instantly generated, so that the van der Waals force effect causing material agglomeration is overcome, the material agglomeration is prevented, and the heterojunction is more easily loaded with nickel nitride particles.
3. When the discharge is finished, the temperature in the quartz tube is rapidly reduced to the room temperature (within 1 second), the agglomeration of the material is effectively prevented again, and the nickel nitride particles are uniformly loaded on the graphene-black phosphorus heterojunction.
Specifically, in step S1), the mass ratio of the red phosphorus powder to the cellulose powder is 1: 1.
if the mass ratio of red phosphorus to cellulose is not equal, the mass ratio of black phosphorus to graphene generated in the electric discharge machining process is not 1: 1, can not be completely compounded into a heterojunction, influences the loading effect of the prepared material and reduces the electrochemical catalytic performance of the product.
Preferably, in step S1), the ultrasonic treatment time is 5-10min, and the mass concentration of the red phosphorus-cellulose combination in the dispersion liquid is 2-10 mg/ml.
If the sonication time is too long, the structure of the material is destroyed, whereas if the sonication time is too short, the mixing of the dispersion is not uniform.
If the mass concentration of the red phosphorus-cellulose conjugate is too low, the production efficiency of the preparation is too low, which is not in accordance with the design object of the present invention, and if the mass concentration of the red phosphorus-cellulose conjugate is too high, the raw material agglomeration is likely to occur, which makes the dispersion liquid be mixed unevenly.
Preferably, in step S2), the mass ratio of the nickel nitride particles to the red phosphorus-cellulose conjugate is 1: (2-10).
If the nickel nitride particles are too few, the nickel nitride particles loaded in the discharge process are too few, and the catalytic activity and stability of the nickel nitride loaded on the black phosphorus-graphene heterojunction are insufficient; if the nickel nitride particles are too large, the nickel nitride particles may be too large to be supported, and thus the optimum catalytic activity may not be exhibited.
Preferably, in the step S2), the rotation speed of stirring is 300-.
If the drying temperature is too low, the evaporation of water is insufficient, and the substance conversion effect in the discharge machining process is further reduced; if the drying temperature is too high, red phosphorus may be burned, and even a fire accident may occur.
Specifically, in step S3), a quartz filler tube 32 is installed in the high-voltage discharge chamber 3, and the quartz filler tube 32 is used for placing the mixture;
the air pressure in the high-voltage discharge cavity 3 is 5-8GPa, the discharge voltage is 300-400V, the discharge capacitance is 270-360mF, the discharge time is less than 2 seconds, and if the discharge time is too long and exceeds 2 seconds, the operation of discharging again is carried out until the time from the beginning to the end of single discharge does not exceed 2 seconds.
The conversion process of the black phosphorus requires high pressure, and the black phosphorus with a lamellar structure cannot be generated due to too low air pressure; the excessive high air pressure brings unnecessary increase to the pressure resistance requirement of the equipment, and leads to the waste of production cost.
When the voltage capacitance is too low, the generated joule heat is not enough to instantaneously raise the temperature to the required temperature, and the current is too low to effectively inhibit the action of coulomb force; when the voltage capacitance is too high, irreversible damage to equipment is easily caused, and the production cost is also improved.
The time from the beginning to the end of the discharge was within 2 seconds and was accompanied by a white flash throughout, which indicated that sufficient carbonization and graphene and black phosphorus generation occurred during the discharge, i.e., above 3000K. If the discharge time is too long and exceeds 2 seconds, the discharge is abnormal, and the re-discharge operation needs to be carried out under the same parameters until the time from the beginning to the end of the single discharge is within 2 seconds.
Under normal conditions, the material resistance of the mixture is within 200 ohms, and the discharge can be completed within two seconds. Therefore, when the discharge is impossible or the discharge time is too long, the position of the quartz filler tube needs to be adjusted according to the same parameters to ensure that the material is fully contacted with the electrode of the quartz filler tube, and the discharge is carried out again.
If the mixture in the quartz filler tube is not compacted, resulting in excessive resistance, or does not make sufficient contact with the electrode to cause disconnection, a re-discharge operation is required.
The phenomenon of overlong discharge occurs because the mixture contains too many impurity components, so that the resistance is large, the material can be fully preheated through multiple discharges, the resistance is reduced after partial carbonization, and finally the effect of rapid discharge which can be completed within two seconds is achieved, so that the effect of discharge machining is realized.
Preferably, in the step S4), the mass concentration of the crude product in the absolute ethyl alcohol is 2-10 mg/ml;
the rotating speed of the centrifuge is 500-700r/min, and the drying temperature is 50-70 ℃.
Experiments prove that the rotating speed of the centrifugal machine is set to be 500-700r/min, and if the rotating speed is too low or too high, the black phosphorus-graphene heterojunction loaded nickel nitride cannot be effectively separated from other materials.
If the drying temperature is too low, the moisture cannot be sufficiently evaporated; if the temperature is too high, the structure of the material is changed, and the loaded nickel nitride particles can be detached.
Furthermore, the invention also provides a preparation device for producing the black phosphorus-graphene heterojunction loaded nickel nitride, which is used for implementing the preparation method for the black phosphorus-graphene heterojunction loaded nickel nitride, and comprises a controller group 1, a high-voltage charging power supply group 2 and a high-voltage discharge cavity 3;
the high-voltage charging power supply group 2 comprises a silicon controlled rectifier component 21, a high-voltage charging power supply 22 and a capacitor group 23;
a quartz filler tube 32 is arranged in the high-voltage discharge cavity 3, and the quartz filler tube 32 is used for placing the mixture;
high-voltage discharge electrodes 31 are arranged at two ends of the quartz filler tube 32, and the two high-voltage discharge electrodes 31 are respectively and electrically connected with the positive electrode and the negative electrode of the high-voltage charging power supply pack 2;
the controller group 1 and the high-voltage charging power supply group 2 are electrically connected, and the controller group 1 is provided with a remote infrared controller.
Specifically, the high-voltage charging power supply 22 charges the capacitor bank 23; the controller group 1 is a key packaging device carrying an embedded chip, the controller group 1 is used for controlling the high-voltage charging power supply 22, starting and stopping of the high-voltage charging power supply 22 can be realized through a remote infrared controller, and charging and discharging parameter values are set; the high-voltage charging power supply group 2 also comprises a silicon controlled rectifier component 21; the switch signal can be released by a key of the remote infrared controller to control the on-off of the controllable silicon component 21, so as to control the on-off of the charging and discharging circuit.
The specific operation method for implementing high-voltage discharge machining is as follows: uniformly filling the mixture into a quartz filler tube 32, clamping the tightly sealed high-voltage discharge cavity 3 by using a high-voltage discharge electrode 31, and switching on an inflator pump 4 to inflate the high-voltage discharge cavity 3 so that the internal air pressure of the high-voltage discharge cavity 3 reaches more than 5 GPa; the controller group 1 is used for controlling the silicon controlled assembly 21 to cut off a connecting loop of the high-voltage discharge cavity 3 and the high-voltage charging power supply group 2, the controller group 1 is used for setting an electrical parameter preset value of the high-voltage charging power supply 22, and the capacitor group of the capacitor group 23 is selected and a switch is closed; a high-voltage charging power supply 22 is switched on to charge the capacitor bank 23; after the charging is finished, the controller group 1 is used for controlling the silicon controlled assembly 21 to be connected with a connecting loop of the high-voltage discharging cavity 3 and the high-voltage charging power supply group 2, and high-voltage discharging is carried out.
The material filled in the quartz filling tube 32 needs to have sufficient conductivity, the resistance value should be less than 100 Ω, and an excessively high resistance may cause discharge failure, so that it is necessary to ensure that the filled material is in sufficient contact with the high-voltage discharge electrode 31 to prevent an open circuit condition from occurring, which may cause discharge failure.
Further, the inner wall of the quartz filler tube 32 is provided with a high temperature resistant coating, and the temperature resistance value of the high temperature resistant coating is greater than 3000K.
The inner surface of the quartz tube filler tube 32 is coated with the high-temperature-resistant coating, the temperature resistance value of the high-temperature-resistant coating can reach more than 3000K, the peak temperature in the discharging process reaches 3000K, and the staying time at the high temperature of 3000K is only several milliseconds, so that the high-temperature-resistant coating can prevent the quartz tube filler tube 32 from being melted at the peak temperature.
Further, the high-voltage discharge cavity 3 is also connected with an inflator pump;
the capacitor bank 23 is formed by combining a plurality of 18mF capacitors; when the capacitor bank 23 is charged, the connection between the high-voltage charging power supply bank 2 and the high-voltage discharging electrode 31 is cut off by the controller bank 1.
The high-pressure discharge cavity is inflated by the inflator pump, so that the air pressure in the high-pressure discharge cavity meets the technological requirements.
The capacitor bank 23 is formed by combining a plurality of 18mF capacitors, and different capacitance values can be selected according to requirements in the discharge machining process to carry out combined discharge.
When the capacitor bank 23 is charged, the connection between the high-voltage charging power supply pack 2 and the high-voltage discharging electrode 31 is cut off through the controller pack 1, so that the production safety is guaranteed.
Examples 1 to 3 and comparative examples 1 to 4
1. The black phosphorus-graphene heterojunction loaded nickel nitride of each example and each comparative example is prepared according to the following steps:
s1) respectively weighing red phosphorus powder and cellulose powder, dispersing in deionized water, and performing ultrasonic treatment to obtain a dispersion liquid containing a red phosphorus-cellulose combination;
s2) adding nickel nitride particles into the dispersion liquid to form a mixed solution, stirring, and putting the stirred mixed solution into a vacuum oven to dry to constant weight to obtain a mixture;
s3) putting the mixture into a high-voltage discharge cavity 3, and performing high-voltage discharge machining to obtain a crude product;
s4) dispersing the crude product in absolute ethyl alcohol, injecting the absolute ethyl alcohol into a centrifuge tube, then placing the centrifuge tube into a centrifuge for centrifugal purification to form a refined product, and then placing the refined product after purification into a vacuum oven to dry to constant weight, so as to obtain the black phosphorus-graphene heterojunction loaded nickel nitride;
in step S1), the mass ratio of red phosphorus powder to cellulose powder is 1: 1;
in the step S1), the ultrasonic treatment time is 5-10min, and the mass concentration of the red phosphorus-cellulose combination in the dispersion liquid is 2-10 mg/ml;
in step S2), the mass ratio of the nickel nitride particles to the red phosphorus-cellulose conjugate is 1: (2-10);
in the step S2), the stirring speed is 300-500r/min, and the drying temperature is 50-70 ℃;
in step S3), a quartz filler tube 32 is installed in the high-voltage discharge chamber 3, and the quartz filler tube 32 is used for placing the mixture;
the air pressure in the high-voltage discharge cavity 3 is 5-8GPa, the discharge voltage is 300-400V, the discharge capacitance is 270-360mF, the discharge time is less than 2 seconds, if the discharge time is longer than more than 2 seconds, the re-discharge operation is carried out until the time from the beginning to the end of single discharge does not exceed 2 seconds;
in step S4), the mass concentration of the crude product in the absolute ethyl alcohol is 2-10 mg/ml; the rotating speed of the centrifuge is 500-700r/min, and the drying temperature is 50-70 ℃.
2. The preparation device for implementing the preparation method comprises a controller group 1, a high-voltage charging power pack 2 and the high-voltage discharge cavity 3;
the high-voltage charging power supply group 2 comprises a silicon controlled rectifier component 21, a high-voltage charging power supply 22 and a capacitor group 23;
a quartz filler tube 32 is arranged in the high-voltage discharge cavity 3 and is used for placing the mixture;
high-voltage discharge electrodes 31 are arranged at two ends of the quartz filler tube 32, and the two high-voltage discharge electrodes 31 are respectively connected with the positive electrode and the negative electrode of the high-voltage charging power supply pack 2;
the controller group 1 comprises a remote infrared controller, and the controller group 1 is electrically connected with the high-voltage charging power supply group 2.
The inner wall of the quartz filler tube is provided with a high-temperature-resistant coating, and the temperature resistance value of the high-temperature-resistant coating is more than 3000K;
the high-voltage discharge cavity is also connected with an inflator pump; the capacitor bank 23 is formed by combining a plurality of 18mF capacitors; when the capacitor bank 23 is charged, the connection between the high-voltage charging power supply bank 2 and the high-voltage discharging electrode 31 is cut off by the controller bank 1.
3. The raw material components and ratios, and process parameters of each example and comparative example are detailed in table 1.
4. The black phosphorus-graphene heterojunction prepared in each example and comparative example is loaded with nitrogenPutting nickel into KOH solution with the mass concentration of 1mol/L, and controlling the current density to be 10mA/cm2The overpotential (mV) and Tafel slope value (mV/dec) of the solution were measured, and the results are shown in Table 1.
TABLE 1 raw material composition, Process parameters and test results of each example and comparative example
It should be noted that the lower the values of the overpotential and the Tafel slope are, the better the electrochemical catalytic activity of the corresponding black phosphorus-graphene heterojunction-supported nickel nitride is.
The overpotential of the HER electrocatalyst which is commercially available at present is close to 1V, and the tafel slope is higher than 100 mV/dec; the potential of the current commercial OER electrocatalyst is higher than 500mV and the tafel slope is higher than 100 mV/dec.
1. According to the detection results of the examples 1 to 3 in the above table 1, the overpotential values of the examples 1 to 3 are 217mV, 233mV and 241mV, respectively, and the corresponding Tafel slope values are 39mV/dec, 44mV/dec and 51mV/dec, respectively, which are lower than the relevant values of each pair of proportions, which indicates that the black phosphorus-graphene heterojunction supported nickel nitride prepared in the examples 1 to 3 has better electrochemical catalytic activity than each pair of proportions, and the overpotential value and the slope value of the example 1 are both minimum values and have the best electrochemical catalytic activity; the values of the overpotential and the Tafel slope of the examples 1 to 3 of the invention are smaller than those of the conventional commercially available HER electrocatalyst or OER electrocatalyst, which indicates that the black phosphorus-graphene heterojunction loaded nickel nitride of the invention has better electrochemical catalytic activity than that of the black phosphorus-graphene heterojunction loaded nickel nitride.
2. Step S1) of comparative example 1, the mass ratio of red phosphorus to cellulose was 1: 2, the proportions of red phosphorus and cellulose are different and differ too much, which results in that the proportion of heterojunction formed in the product is reduced, the values of overpotential and Tafel slope of comparative example 1 are greatly increased compared with that of example 1, and the electrochemical catalytic activity of corresponding comparative example 1 is also reduced.
3. Step S2) of comparative example 2, the mass ratio of nickel nitride particles to red phosphorus-cellulose conjugate was 1: 1.5, the nickel nitride content is too high, so that the loading rate of the nickel nitride of the two-dimensional lamellar unit in the reaction process is too high, the electric mobility of the material is inhibited, the overpotential and Tafel slope values of the comparative example 2 are obviously improved compared with those of the example 1, and the electrochemical catalytic activity of the corresponding comparative example 2 is also obviously reduced.
4. Comparative example 3 the mass ratio of red phosphorus to cellulose was 1: 0.5, although the mass ratio of the red phosphorus-cellulose combination to the nickel nitride particles is increased in the step S2), the ratio of the red phosphorus to the cellulose is different, the cellulose ratio is low, the ratio of the formed graphene to the heterojunction in the product is obviously reduced, the values of the overpotential and the Tafel slope of the comparative example 3 are obviously increased compared with those of the example 1, and the electrochemical catalytic activity of the corresponding comparative example 3 is also obviously reduced and is poor.
5. Step S2) of comparative example 4, the mass ratio of nickel nitride particles to red phosphorus-cellulose conjugate was 1: 12, the content of nickel nitride is too small, so that the nickel nitride particles loaded in the discharging process are too small, the catalytic activity of the prepared black phosphorus-graphene heterojunction-loaded nickel nitride is poor, and the stability is insufficient, so that the values of the overpotential and the Tafel slope of the corresponding comparative example 4 are greatly increased compared with the value of the example 1, and the product of the comparative example 4 has almost no electrochemical catalytic activity.
In summary, in the preparation method of the black phosphorus-graphene heterojunction loaded nickel nitride, red phosphorus and cellulose are used as raw materials to prepare a carrier of the heterojunction formed by the black phosphorus and the graphene, then nickel nitride particles are loaded, and the nickel nitride particles are uniformly distributed on a lamellar heterojunction substrate formed by the black phosphorus and the graphene and used as an electrocatalyst of an OER oxygen evolution reaction, so that the nickel nitride-loaded black phosphorus-graphene heterojunction has good electrocatalytic activity in an alkaline environment.
The invention implements accurate discharge processing aiming at the formula material, in the discharge process, the raw material is converted into graphene and black phosphorus in millisecond-level time unit, and a heterojunction is formed, and meanwhile, nickel nitride particles are also loaded on a lamellar structure of the heterojunction, so that the method has the characteristics of low cost and high stability, and the method has the advantages of simple process, no secondary pollution, high production efficiency and short discharge time, and can prepare large-batch products in a shorter production period.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples" or the like mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
The technical principle of the present invention is described above in connection with specific embodiments. The description is only intended to explain the principles of the invention; and should not be construed as limiting the scope of the invention in any way. Based on the explanations herein; other embodiments of the invention will occur to those skilled in the art without the exercise of inventive faculty; all of which fall within the scope of the present invention.
Claims (10)
1. A preparation method of black phosphorus-graphene heterojunction loaded nickel nitride is characterized by comprising the following steps:
s1) respectively weighing red phosphorus powder and cellulose powder, dispersing in deionized water, and performing ultrasonic treatment to obtain a dispersion liquid containing a red phosphorus-cellulose combination;
s2) adding nickel nitride particles into the dispersion liquid to form a mixed solution, stirring, and putting the stirred mixed solution into a vacuum oven to dry to constant weight to obtain a mixture;
s3) putting the mixture into a high-voltage discharge cavity, and performing high-voltage discharge processing to obtain a crude product;
s4) dispersing the crude product in absolute ethyl alcohol, injecting the absolute ethyl alcohol into a centrifugal tube, placing the centrifugal tube into a centrifuge for centrifugal purification to form a refined product, and then placing the refined product after purification into a vacuum oven to dry to constant weight, so that the black phosphorus-graphene heterojunction loaded nickel nitride is prepared.
2. The method for preparing black phosphorus-graphene heterojunction supported nickel nitride according to claim 1, wherein in step S1), the mass ratio of red phosphorus powder to cellulose powder is 1: 1.
3. the method for preparing black phosphorus-graphene heterojunction loaded nickel nitride according to claim 1, wherein in step S1), the time of ultrasonic treatment is 5-10min, and the mass concentration of the red phosphorus-cellulose combination in the dispersion liquid is 2-10 mg/ml.
4. The method for preparing black phosphorus-graphene heterojunction supported nickel nitride according to claim 1, wherein in step S2), the mass ratio of the nickel nitride particles to the red phosphorus-cellulose combination is 1: (2-10).
5. The method as claimed in claim 1, wherein in step S2), the rotation speed of stirring is 300-500r/min, and the drying temperature is 50-70 ℃.
6. The method for preparing black phosphorus-graphene heterojunction loaded nickel nitride according to claim 1, wherein in step S3), a quartz filler tube is installed in the high-voltage discharge chamber, and the quartz filler tube is used for placing the mixture;
the air pressure in the high-voltage discharge cavity is 5-8GPa, the discharge voltage is 300-400V, the discharge capacitance is 270-360mF, the discharge time is less than 2 seconds, and if the discharge time is too long and exceeds 2 seconds, the re-discharge operation is carried out until the time from the beginning to the end of single discharge does not exceed 2 seconds.
7. The method for preparing black phosphorus-graphene heterojunction-supported nickel nitride according to claim 1, wherein in step S4), the mass concentration of the crude product in absolute ethanol is 2-10 mg/ml;
the rotating speed of the centrifuge is 500-700r/min, and the drying temperature is 50-70 ℃.
8. A preparation device for producing black phosphorus-graphene heterojunction loaded nickel nitride is used for implementing the preparation method of black phosphorus-graphene heterojunction loaded nickel nitride according to any one of claims 1 to 7, and comprises a controller group, a high-voltage charging power supply group and the high-voltage discharge cavity;
the high-voltage charging power supply group comprises a silicon controlled rectifier component, a high-voltage charging power supply and a capacitor group;
a quartz filler tube is arranged in the high-voltage discharge cavity and used for placing the mixture;
high-voltage discharge electrodes are arranged at two ends of the quartz filler tube, and the two high-voltage discharge electrodes are respectively and electrically connected with positive and negative electrodes of the high-voltage charging power supply pack;
the controller group with high voltage charging power supply group electric connection, the controller group is equipped with long-range infrared controller.
9. The preparation device for producing the black phosphorus-graphene heterojunction-loaded nickel nitride as claimed in claim 8, wherein the inner wall of the quartz filler tube is provided with a high-temperature-resistant coating, and the temperature resistance value of the high-temperature-resistant coating is more than 3000K.
10. The device for preparing the black phosphorus-graphene heterojunction-loaded nickel nitride according to claim 8, wherein the high-pressure discharge cavity is further connected with an inflator pump;
the capacitor bank is formed by combining a plurality of groups of 18mF capacitors; when the capacitor bank is charged, the connection between the high-voltage charging power supply pack and the high-voltage discharging electrode is cut off through the controller bank.
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