WO2020119579A1 - 一种二硼化钛/碳化硼复合电极及其制备方法与应用 - Google Patents

一种二硼化钛/碳化硼复合电极及其制备方法与应用 Download PDF

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WO2020119579A1
WO2020119579A1 PCT/CN2019/123439 CN2019123439W WO2020119579A1 WO 2020119579 A1 WO2020119579 A1 WO 2020119579A1 CN 2019123439 W CN2019123439 W CN 2019123439W WO 2020119579 A1 WO2020119579 A1 WO 2020119579A1
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boron carbide
titanium diboride
substrate
composite coating
composite electrode
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PCT/CN2019/123439
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English (en)
French (fr)
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唐永炳
徐梦琦
杨扬
胡渊
张文军
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深圳先进技术研究院
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33—Electric or magnetic properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/02—Boron; Borides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/02—Boron; Borides
    • C01B35/04—Metal borides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present application belongs to the technical field of electrochemical catalysis, and in particular relates to a titanium diboride/boron carbide composite electrode and a preparation method and application thereof.
  • Ammonia has a very important role in human society. It can not only be used in chemical production, but also promote the growth of crops.
  • the use of electrocatalytic nitrogen reduction to generate ammonia (Nitrogen Reduction) (NRR) technology is an effective solution. Whether the electrocatalytic reduction can be performed efficiently has high requirements on the catalytic activity of the electrode.
  • the hydrogen evolution reaction is easier to perform than the NRR reaction, and the NRR reaction is often accompanied by side reactions. The above reasons restrict the conversion rate of ammonia.
  • Electrodes such as nickel, cobalt, or platinum
  • other compounds such as Fe2O3-CNT, Fe3O4, or MoS2
  • the above electrode materials still have many disadvantages. For example, low catalytic activity, poor electrode material stability, by-product formation during the reaction, and high cost. Therefore, there is no efficient and safe electrode that can be used to catalyze the reduction of nitrogen to form ammonia.
  • the present application provides a titanium diboride/boron carbide composite electrode and a preparation method and application thereof.
  • the conductivity and catalytic activity of the electrode are improved.
  • a first aspect of the present application provides a titanium diboride/boron carbide composite electrode, which includes a substrate and a composite coating provided on the substrate, the composite coating including titanium diboride and boron carbide.
  • the titanium diboride coating can effectively improve the conductivity of the composite coating; and the incorporation of boron carbide can effectively improve the composite coating Of catalytic activity. Therefore, the titanium diboride/boron carbide composite electrode can effectively improve the conductivity and catalytic activity, and greatly increase the yield of electrocatalytic reduction of nitrogen to ammonia.
  • the composite coating includes a flat structure layer disposed on the substrate and an array protrusion structure provided on the surface of the flat structure layer.
  • the shape of the array protrusion is prism, pyramid, cone or needle.
  • the shape of the array protrusion is a pyramid, a cone, or a needle; the top radius of the array protrusion of the pyramid, cone, or needle is 50-500 nm.
  • the content of the boron carbide gradually increases from the side close to the base to the side far from the base.
  • the mass fraction of the titanium diboride in the composite coating is 1-50%, and the mass fraction of the boron carbide is 50-99%.
  • the thickness of the composite coating is 600nm-6 ⁇ m, and the height of the array protrusion is 50-500nm.
  • the second aspect of the present application provides a method for preparing a titanium diboride/boron carbide composite electrode, including:
  • the composite coating including titanium diboride and boron carbide to obtain a titanium diboride/boron carbide composite electrode.
  • the preparation method provided in the second aspect of the present application can prepare a titanium diboride/boron carbide composite electrode with excellent performance of electrocatalytic nitrogen reduction to generate ammonia gas through a simple process.
  • the preparation is simple, the cost is low, and under severe conditions The service life is high and it has strong practicality.
  • the composite coating after the composite coating is deposited on the substrate after cleaning, it also includes etching the surface layer of the composite coating to form an array convex structure, so that the composite coating includes the substrate provided on the substrate.
  • the flat structure layer and the array convex structure provided on the surface of the flat structure layer obtain a titanium diboride/boron carbide composite electrode.
  • the third aspect of the present application provides the application of the titanium diboride/boron carbide composite electrode provided in the first aspect of the present application in electrocatalytic reduction of nitrogen.
  • the titanium diboride/boron carbide composite electrode provided in the first aspect of the present application is used to electrically catalyze the reduction of ammonia gas by nitrogen, and the catalytic efficiency and catalytic yield are higher.
  • FIG. 1 is a schematic structural diagram of a titanium diboride/boron carbide composite electrode in an embodiment of the present application
  • FIG. 2 is a schematic structural diagram of a titanium diboride/boron carbide composite electrode in another embodiment of the present application.
  • FIG. 3 is a schematic structural diagram of a titanium diboride/boron carbide composite electrode in another embodiment of the present application.
  • FIG. 4 is a schematic structural diagram of the change of the content of boron carbide in the titanium diboride/boron carbide composite electrode in the embodiment of the present application;
  • FIG. 5 is a schematic structural diagram of a change in the content of boron carbide in the titanium diboride/boron carbide composite electrode in another embodiment of the present application;
  • FIG. 6 is a flow chart of the preparation process of the titanium diboride/boron carbide composite electrode in the embodiment of the present application.
  • FIG. 7 is a schematic structural diagram of a dual-cell reactor in an embodiment of the present application.
  • a titanium diboride/boron carbide composite electrode provided by an embodiment of the present application includes a substrate 1 and a composite coating 2 provided on the substrate 1, the composite coating 2 includes diboride Titanium and boron carbide 23.
  • a titanium diboride/boron carbide composite electrode provided by an embodiment of the present application has a high catalytic activity of boron carbide 23, which can effectively promote the catalytic nitrogen reaction, but pure boron carbide 23 has poor conductivity and may reverse Come to affect the catalytic efficiency. While titanium diboride has excellent conductivity, but pure titanium diboride has poor catalytic performance. Therefore, boron carbide 23 and titanium diboride are compounded together to form a composite coating 2 to give full play to their respective advantages. By combining their properties, a composite coating with excellent electrical conductivity and catalytic performance can be obtained 2 and titanium diboride/boron carbide composite electrode.
  • the composite coating 2 is provided on one surface of the substrate 1 or the opposite surfaces of the substrate 1.
  • the composite coating 2 of the present application is provided on the surfaces of opposite sides of the substrate 1 to further improve the catalytic performance of the titanium diboride/boron carbide composite electrode.
  • the titanium diboride/boron carbide composite electrode further includes an electrode active material layer provided on the surface of the composite coating 2.
  • the composite coating 2 containing the matrix 1 can serve as a current collector in the electrode, and an active material layer is coated on the surface of the composite coating 2 to form an electrode together.
  • the material of the substrate 1 includes one or more of titanium and silicon.
  • the substrate 1 in this application may be a titanium substrate, a titanium mesh or a silicon wafer. More preferably, the substrate in this application may be a titanium mesh.
  • the titanium mesh with a mesh structure has a larger specific surface area, which can improve the bonding force between the composite coating 2 and the substrate 1.
  • the composite coating 2 is deposited on a three-dimensional mesh-like titanium mesh, the specific surface area of the composite coating 2 is also increased, and the active site of the composite coating 2 is further increased, which further enhances diboron to a certain extent. Catalytic performance of titanium carbide/boron carbide composite electrode. More preferably, the substrate 1 is a 50-200 mesh titanium mesh.
  • the composite coating 2 includes a flat structure layer 21 disposed on the substrate 1 and an array protrusion 22 structure provided on the surface of the flat structure layer 21 .
  • the composite protrusion 2 of the array protrusion 22 structure has the structural advantage of orientation, which not only greatly improves its specific surface area, but also exposes more active sites and increases The ability of electrocatalytic reduction of nitrogen is increased, thereby improving the catalytic efficiency.
  • the array protrusion 22 is vertically arranged on the flat structure layer 21.
  • the shape of the array protrusion 22 is a prism, a pyramid, a cone, or a needle.
  • the shape of the array protrusion 22 is a prism, as shown in FIG. 2, when the shape of the array protrusion 22 is a pyramid, a cone, or a needle, as shown in FIG. 3.
  • the shape of the array protrusion 22 is a pyramid, a cone, or a needle.
  • the tip (the end away from the base 1) of the pyramid-shaped, conical, or needle-shaped array protrusion 22 is a tip.
  • the array protrusion 22 with a tip can play a role of gathering electrons, making the transmission and circulation of electrons easier.
  • a plurality of protrusions of the pyramid-shaped, cone-shaped, or needle-shaped array protrusions 22 are spaced or closely connected. More preferably, the plurality of protrusions of the pyramid-shaped, cone-shaped, or needle-shaped array protrusions 22 are closely connected.
  • the shape of the array protrusion 22 is a pyramid, a cone, or a needle; the top curvature radius of the array protrusion 22 of a pyramid, a cone, or a needle is 50-500 nm.
  • the tip of a pyramid, cone, or needle (such as the end of the array protrusion 2222 away from the flat structure layer 2121 in Figure 3) is not a point, but has a certain radius of curvature. These sharp nanotips will significantly amplify the local electric field, thus An electric field enhancement effect is generated, and a high electric field may enhance the concentration of the reagent near the tip of the electrode, realize the enrichment of alkali metal ions, and significantly improve the catalytic efficiency of the electrode.
  • the radius of curvature of the tip of the array protrusion 22 in a pyramid, cone or needle shape is 100-400 nm. More preferably, the radius of curvature of the tip of the array protrusion 22 in a pyramid, cone or needle shape is 200-300 nm.
  • the content of the boron carbide 23 gradually increases from the side close to the base 1 to the side far from the base 1 increase.
  • the boron carbide 23 in the composite coating 2 of the present application is not evenly distributed, because boron carbide 23 can improve the catalytic activity, and the most applied part of the electrode during use is the surface of the electrode, and the NRR reaction is also carried out on the surface of the electrode.
  • the content of boron carbide 23 gradually increases from the side close to the base 1 to the side far from the base 1 not only can the binding force of the composite coating 2 and the base 1 be improved, but also the surface of the composite coating 2 can be carbonized
  • the increased content of boron 23 further improves the catalytic activity of the titanium diboride/boron carbide composite electrode.
  • the mass fraction of the titanium diboride in the composite coating 2 is 1-50%, and the mass fraction of the boron carbide 23 is 50-99%. Since titanium diboride has excellent electrical conductivity, but poor catalytic performance, boron carbide 23 has excellent catalytic performance, and poor electrical conductivity. Therefore, it can be found from the above that titanium diboride and boron carbide 23 will affect each other, too much content of titanium diboride will reduce the catalytic performance of the titanium diboride/boron carbide composite electrode, while the content of boron carbide 23 is too Usually affect the conductivity of the electrode. Therefore, the content of titanium diboride and boron carbide 23 is not a simple superposition.
  • Titanium diboride and boron carbide 23 are a whole and are indivisible independently. Therefore, it is only necessary that the mass fraction of the titanium diboride in the composite coating 2 is 1-50%, and the mass fraction of the boron carbide 23 is 50-99%, in order to obtain titanium diboride/boron carbide with excellent comprehensive performance Compound electrode.
  • the mass fraction of the titanium diboride in the composite coating 2 is 10-40%, and the mass fraction of the boron carbide 23 is 60-90%. More preferably, the mass fraction of the titanium diboride in the composite coating 2 is 20-30%, and the mass fraction of the boron carbide 23 is 70-80%.
  • the thickness of the composite coating 2 is 600 nm-6 ⁇ m, and the height of the array protrusion 22 is 50-500 nm.
  • a composite coating 2 of 600 nm-6 ⁇ m can be finally prepared.
  • the height of the array protrusion 22 is 50-500 nm, and the remaining thickness is the thickness of the flat layer.
  • the thickness of the composite coating 2 is 1 ⁇ m-5 ⁇ m, and the height of the array protrusion 22 is 100-400 nm. More preferably, the thickness of the composite coating 2 is 2 ⁇ m-4 ⁇ m, and the height of the array protrusion 22 is 200-300 nm.
  • a method for preparing a titanium diboride/boron carbide composite electrode provided by an embodiment of the present application includes:
  • the composite coating 2 includes titanium diboride and boron carbide 23 to obtain titanium diboride/ Boron carbide composite electrode.
  • the preparation method provided in the embodiments of the present application can prepare a titanium diboride/boron carbide composite electrode with excellent performance of electrocatalytic nitrogen reduction to generate ammonia gas through a simple process.
  • the preparation is simple, the cost is low, and it is used in harsh conditions The life is high, and it has strong practicality.
  • a composite coating 2 is deposited on the substrate 1 after cleaning.
  • the background vacuum is evacuated to 10 -3 Pa
  • the ion source is turned off
  • the angle valve is adjusted to 90
  • the bias voltage Adjust to 30-80V adjust the flow of argon to 200-400sccm, set the target power of carbon target and titanium diboride target to 1500-2500W, the target current to 4.5-6A, then turn on the carbon target and diboron Titanium target, coating 10-30min.
  • the method further includes etching the surface layer of the composite coating layer 2 to form an array protrusion 22 structure to make the composite coating layer
  • the layer 2 includes a flat structure layer 21 provided on the substrate 1 and an array protrusion 22 structure provided on the surface of the flat structure layer 21 to obtain a titanium diboride/boron carbide composite electrode.
  • This application uses DC plasma etching technology for etching.
  • the etching operation is finally performed.
  • the substrate 1 with the titanium diboride/boron carbide 23 composite coating 2 deposited on the surface is placed in a hot wire chemical vapor deposition equipment, using a diameter A 0.5 mm tantalum wire is used as the filament, and the temperature of the tantalum wire is heated to 1500-3000°C.
  • the distance between the tantalum wire and the base 1 is adjusted to 8 mm, so that the temperature of the base 1 is 600-1000°C.
  • a negative bias voltage of 200-400V is applied to the substrate 1 to generate glow discharge using a DC constant voltage source for etching.
  • the gases introduced include methane and hydrogen, the volume ratio of methane and hydrogen is (1-5): (90-100), the etching pressure is 10-20torr, the etching temperature is 600-1000°C, and the etching time is 2-6h, finally get the titanium diboride/boron carbide composite electrode.
  • the titanium diboride/boron carbide composite electrode provided in the examples of the present application in electrocatalytic reduction of nitrogen.
  • the titanium diboride/boron carbide composite electrode provided in the embodiments of the present application is used to electrically catalyze the reduction of ammonia gas by nitrogen, and the catalytic efficiency and catalytic yield are high.
  • the titanium diboride/boron carbide composite electrode provided by the embodiment of the present application can also be used for electrocatalytic reduction of carbon dioxide, oxygen reduction, methanol oxidation and other electrochemical reactions, and also has high catalytic activity.
  • An embodiment of the present application provides a dual-cell reactor for catalyzing the reduction of nitrogen to form ammonia, which is characterized by comprising a working electrode 112, a counter electrode 111 and a reference electrode 113.
  • the working electrode 112 includes The titanium diboride/boron carbide composite electrode provided in the example.
  • the titanium diboride/boron carbide composite electrode is applied to a dual-cell reactor, in which the anode chamber 101 and the cathode chamber 112 are separated by a proton exchange membrane 103.
  • the titanium diboride/boron carbide composite electrode of the embodiment of the present application is used as the working electrode 112
  • the graphite rod is the counter electrode 111
  • the Ag/AgCl is the reference electrode 113.
  • the working electrode 112 and the reference electrode 113 are located in the cathode chamber 102
  • the counter electrode 111 is located in the anode chamber 101, and is connected to the voltmeter 114
  • the working electrode and the counter electrode are separated by 2-5cm.
  • the power source 104 is connected to the working electrode 112, the counter electrode 111, the reference electrode 113, and the voltmeter 114, respectively.
  • the cathode chamber 102 is provided with an air inlet 115 and an air outlet 116.
  • the gas inlet 115 is used for introducing nitrogen
  • the gas outlet 116 is used for removing excess nitrogen.
  • Step 1 Wash the titanium mesh in acetone, absolute alcohol and deionized water for 10 minutes, and then dry in the oven overnight.
  • Step 2 Fix the titanium mesh on the baffle and suspend it in the magnetron sputtering equipment, keep the substrate parallel and directly facing the target, the distance between the target and the substrate surface is 8cm, and set the rotation speed of the titanium mesh 2r/min. Then perform the evacuation operation. During the evacuation process, first open the mechanical pump and the rough extraction valve, open the maintenance valve when the pressure of the deposition chamber of the magnetron sputtering equipment is pumped to 10Pa, and pump the pressure of the deposition chamber to 4Pa , Then close the coarse pumping valve, open the high valve, and finally pump the deposition chamber to 5 ⁇ 10 -3 Pa.
  • Step 3 Subsequently, the target and the sample are cleaned.
  • the carbon target and the titanium diboride target are opened, 300 sccm of argon gas is introduced, and the cleaning is performed for 5 minutes.
  • the flow rate of argon gas was adjusted to 500 sccm
  • the bias voltage was set to 800 V
  • the cleaning was performed for 5 minutes.
  • adjust the angle valve to 45, turn on the ion source, adjust the flow of argon to 300 sccm, adjust the bias to 150 V, and clean for 20 min.
  • Step 4 Deposit the composite coating 2 on the cleaned titanium mesh.
  • vacuum the background to 10 -3 Pa turn off the ion source, adjust the angle valve to 90, and adjust the bias voltage to 30V.
  • the flow rate of argon gas was adjusted to 200 sccm
  • the target power of the carbon target and the titanium diboride target was set to 1500 W
  • the target current was set to 4.5 A
  • the carbon target and the titanium diboride target were turned on, and the coating was performed for 10 min. After the coating is completed, face the other side of the titanium mesh directly to the target, and repeat steps 2 to 4.
  • Step 5 Finally, perform the etching operation.
  • the titanium mesh with titanium diboride/boron carbide 23 composite coating 2 deposited on the surface is placed in the hot wire chemical vapor deposition equipment, using a 0.5mm diameter
  • the tantalum wire is used as the filament, and the temperature of the tantalum wire is heated to 1500°C.
  • the distance between the tantalum wire and the titanium mesh is adjusted to 8 mm, so that the temperature of the titanium mesh is 600°C.
  • a negative bias voltage of 200V is applied on the titanium mesh to generate glow discharge using a DC constant voltage source for etching.
  • the gases introduced include methane and hydrogen, the volume ratio of methane and hydrogen is 1:100, the etching pressure is 10torr, the etching temperature is 600°C, the etching time is 2h, and finally the titanium diboride/boron carbide composite is obtained electrode.
  • Step 1 Wash the titanium sheet in acetone, absolute alcohol and deionized water for 20 minutes, and then dry in the oven overnight.
  • Step 2 Fix the titanium sheet on the baffle and suspend it in the magnetron sputtering equipment, keep the substrate parallel and directly facing the target, the distance between the target and the substrate surface is 20cm, and set the rotation speed of the titanium sheet 2r/min. Then perform the evacuation operation. During the evacuation process, first open the mechanical pump and the rough extraction valve, open the maintenance valve when the pressure of the deposition chamber of the magnetron sputtering equipment is pumped to 10Pa, and pump the pressure of the deposition chamber to 4Pa Then, close the coarse pumping valve, open the high valve, and finally pump the deposition chamber to 6 ⁇ 10 -3 Pa.
  • Step 3 The target and the sample are subsequently cleaned.
  • the carbon target and the titanium diboride target are opened, 300 sccm of argon gas is introduced, and the cleaning is performed for 10 minutes.
  • the flow rate of argon gas was adjusted to 500 sccm
  • the bias voltage was set to 800 V
  • the cleaning was performed for 10 min.
  • adjust the angle valve to 45, turn on the ion source, adjust the flow of argon to 300 sccm, adjust the bias to 150 V, and clean for 20 min.
  • Step 4 Deposit the composite coating 2 on the cleaned titanium sheet.
  • vacuum the background to 10 -3 Pa turn off the ion source, adjust the angle valve to 90, and adjust the bias voltage to 80V.
  • the flow rate of argon gas was adjusted to 400 sccm
  • the target power of the carbon target and the titanium diboride target was set to 2500 W
  • the target current was set to 6 A
  • the carbon target and the titanium diboride target were turned on, and the coating was performed for 30 min. After the coating is completed, the other side of the titanium sheet is directly opposed to the target, and steps 2 to 4 are repeated.
  • Step 5 Finally, the etching operation is carried out.
  • the titanium plate with titanium diboride/boron carbide 23 composite coating 2 deposited on the surface is placed in the hot wire chemical vapor deposition equipment, using a 0.5mm diameter
  • the tantalum wire is used as a filament, and the temperature of the tantalum wire is heated to 3000°C.
  • the distance between the tantalum wire and the titanium sheet is adjusted to 8 mm, so that the temperature of the titanium sheet is 1000°C.
  • a negative bias voltage of 400V is applied to the titanium sheet to generate glow discharge using a DC constant voltage source for etching.
  • the gases introduced include methane and hydrogen, the volume ratio of methane and hydrogen is 5:90, the etching pressure is 20torr, the etching temperature is 1000°C, and the etching time is 6h, and finally the titanium diboride/boron carbide composite is obtained electrode.
  • Step 1 Wash the silicon wafers in acetone, absolute alcohol and deionized water for 15 minutes, and then dry in the oven overnight.
  • Step 2 Fix the silicon wafer on the baffle and suspend it in the magnetron sputtering equipment, keep the substrate parallel and directly facing the target, the distance between the target and the substrate surface is 15cm, and set the speed of the silicon wafer 2r/min. Then perform the evacuation operation. During the evacuation process, first open the mechanical pump and the rough extraction valve, open the maintenance valve when the pressure of the deposition chamber of the magnetron sputtering equipment is pumped to 10Pa, and pump the pressure of the deposition chamber to 4Pa , Then close the coarse pumping valve, open the high valve, and finally pump the deposition chamber to 5.5 ⁇ 10 -3 Pa.
  • Step 3 The target and the sample are subsequently cleaned.
  • the carbon target and the titanium diboride target are opened, 300 sccm of argon gas is introduced, and the cleaning is performed for 10 minutes.
  • the flow rate of argon gas was adjusted to 500 sccm
  • the bias voltage was set to 800 V
  • the cleaning was performed for 10 min.
  • adjust the angle valve to 45, turn on the ion source, adjust the flow of argon to 300 sccm, adjust the bias to 150 V, and clean for 20 min.
  • Step 4 Deposit the composite coating 2 on the cleaned silicon wafer.
  • vacuum the background to 10 -3 Pa turn off the ion source, adjust the angle valve to 90, and adjust the bias voltage to 50V.
  • the flow rate of argon gas was adjusted to 300 sccm
  • the target power of the carbon target and the titanium diboride target was set to 2000 W
  • the target current was set to 5.3 A
  • the carbon target and the titanium diboride target were turned on, and the coating was performed for 20 min. After the coating is completed, face the other side of the titanium mesh directly to the target, and repeat steps 2 to 4.
  • Step 5 Finally, the etching operation is carried out.
  • the silicon wafer with titanium diboride/boron carbide 23 composite coating 2 deposited on the surface is placed in the hot wire chemical vapor deposition equipment, using a 0.5mm diameter
  • the tantalum wire is used as the filament, and the temperature of the tantalum wire is heated to 2100°C.
  • the distance between the tantalum wire and the silicon wafer is adjusted to 8 mm, so that the temperature of the silicon wafer is 800°C.
  • a negative bias voltage of 300V is applied to the silicon wafer to generate glow discharge using a DC constant voltage source for etching.
  • the gases introduced include methane and hydrogen, the volume ratio of methane and hydrogen is 1.5:98, the etching pressure is 15torr, the etching temperature is 800°C, the etching time is 4h, and finally the titanium diboride/boron carbide composite is obtained electrode.
  • the titanium diboride/boron carbide composite electrode obtained in Example 1-3 was made into a dual-cell reactor. Using a three-electrode system, the successfully etched titanium diboride/boron carbide composite electrode is used as the working electrode 112, the graphite rod is the counter electrode 111, Ag/AgCl is the reference electrode 113, and the working electrode 112 and the counter electrode 111 are separated by 2cm. The reference electrode 113 is close to the working electrode 112. A saturated 0.1 M HCl solution was added to the cathode chamber 101, and an equal volume of 0.1 M HCl solution was added to the anode chamber 112.
  • the titanium diboride/boron carbide composite electrode obtained in Example 1-3 has excellent electrocatalytic nitrogen reduction to generate ammonia gas
  • the titanium diboride obtained in Example 3/ The electrocatalytic reduction of boron carbide composite electrode to produce ammonia gas has the best performance, has the highest Faraday efficiency, ammonia gas yield and cycle number, and has strong practicability.

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Abstract

本申请提供了一种二硼化钛/碳化硼复合电极及其制备方法与应用，其中，二硼化钛/碳化硼复合电极包括基体以及设于所述基体上的复合涂层，所述复合涂层包括二硼化钛和碳化硼。二硼化钛涂层可有效地提高复合涂层的导电性；而碳化硼的掺入，可有效地提高复合涂层的催化活性。因此二硼化钛/碳化硼复合电极可有效地提高导电性和催化活性，极大地提高电催化氮气还原生成氨气的产量。本申请还提供了二硼化钛/碳化硼复合电极的制备方法，通过简单的工艺便可制备出催化性能优异的二硼化钛/碳化硼复合电极，简化了制备步骤，降低了成本。本申请还提供了将二硼化钛/碳化硼复合电极应用在电催化还原氮气中。

Description

一种二硼化钛/碳化硼复合电极及其制备方法与应用 技术领域
本申请属于电化学催化技术领域，具体涉及一种二硼化钛/碳化硼复合电极及其制备方法与应用。
背景技术
氨气对人类社会有着非常重要的作用。它不仅可以用于化工生产，还可以促进农作物的生长。采用电催化氮气还原生成氨气(Nitrogen Reduction Reaction，NRR)技术是一种行之有效的解决办法。电催化还原是否能够高效的进行，对电极的催化活性有着很高的要求；同时在水系溶液中，析氢反应相较于NRR反应更容易进行，并且NRR反应还经常伴随着副反应的产生。上述原因都制约着氨气的转化率。
目前，通常采用贵金属(如镍、钴或铂)或者是其他化合物(如Fe2O3－CNT、Fe3O4或MoS2)作为电极，但上述电极材料还是有着诸多的缺点。例如催化活性低、电极材料稳定性差、反应过程中生成副产物、成本高。因此，现在还并没有一种高效、安全的可用于催化氮气还原生成氨气的电极。
申请内容
鉴于此，本申请提供了一种二硼化钛/碳化硼复合电极及其制备方法与应用，通过在同时掺入二硼化钛和氮化硼，提高电极的导电性和催化活性。
本申请第一方面提供了一种二硼化钛/碳化硼复合电极，包括基体以及设于所述基体上的复合涂层，所述复合涂层包括二硼化钛和碳化硼。
本申请第一方面提供的一种二硼化钛/碳化硼复合电极，二硼化钛涂层可 有效地提高复合涂层的导电性；而碳化硼的掺入，可有效地提高复合涂层的催化活性。因此二硼化钛/碳化硼复合电极可有效地提高导电性和催化活性，极大地提高电催化氮气还原生成氨气的产量。
其中，所述复合涂层包括设置于所述基体上的平整结构层和设置于所述平整结构层表面的阵列凸起结构。
其中，所述阵列凸起的形状为棱柱、棱锥、圆锥或针状。
其中，所述阵列凸起的形状为棱锥、圆锥或针状；棱锥、圆锥或针状的所述阵列凸起的顶端曲率半径为50-500nm。
其中，在所述复合涂层中，所述碳化硼的含量由靠近所述基体的一侧至远离所述基体的一侧逐渐增加。
其中，所述复合涂层中所述二硼化钛的质量分数为1-50％，所述碳化硼的质量分数为50-99％。
其中，所述复合涂层的厚度为600nm-6μm，所述阵列凸起的高度为50-500nm。
本申请第二方面提供了一种二硼化钛/碳化硼复合电极的制备方法，包括：
取基体，对所述基体进行清洗操作，在清洗后的所述基体上沉积复合涂层，所述复合涂层包括二硼化钛和碳化硼，得到二硼化钛/碳化硼复合电极。
本申请第二方面提供的制备方法，通过简单的工艺即可制备出电催化氮气还原生成氨气性能优异的二硼化钛/碳化硼复合电极，制备简单，成本低廉，在较恶劣的情况下使用寿命较高，具有很强的实用性。
其中，在清洗后的所述基体上沉积复合涂层之后，还包括在所述复合涂层的表层进行刻蚀以形成阵列凸起结构，使所述复合涂层包括设置于所述基体上 的平整结构层和设置于所述平整结构层表面的阵列凸起结构，得到二硼化钛/碳化硼复合电极。
本申请第三方面提供了本申请第一方面提供的二硼化钛/碳化硼复合电极在电催化还原氮气中的应用。
本申请第三方面利用本申请第一方面提供的二硼化钛/碳化硼复合电极来电催化氮气还原氨气，催化效率、催化产量较高。
附图说明
为了更清楚地说明本申请实施例中的技术方案，下面将对本申请实施例中所需要使用的附图进行说明。
图1为本申请实施例中二硼化钛/碳化硼复合电极的结构示意图；
图2为本申请另一实施例中二硼化钛/碳化硼复合电极的结构示意图；
图3为本申请另一实施例中二硼化钛/碳化硼复合电极的结构示意图；
图4为本申请实施例中二硼化钛/碳化硼复合电极中碳化硼的含量变化的结构示意图；
图5为本申请另一实施例中二硼化钛/碳化硼复合电极中碳化硼的含量变化的结构示意图；
图6为本申请实施例中二硼化钛/碳化硼复合电极的制备工艺流程图；
图7为本申请实施例中双电池反应器的结构示意图。
具体实施方式
以下是本申请的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本申请原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本申请的保护范围。
请参考图1，本申请实施例提供的一种二硼化钛/碳化硼复合电极，包括基体1以及设于所述基体1上的复合涂层2，所述复合涂层2包括二硼化钛和碳化硼23。
本申请实施例提供的一种二硼化钛/碳化硼复合电极，碳化硼23的催化活性较高，可有效地促进催化氮气反应，但纯的碳化硼23的导电性较差，又会反过来影响催化效率。而二硼化钛的导电性能优异，但纯的二硼化钛的催化性能较差。因此将碳化硼23和二硼化钛复合在一起，形成复合涂层2，充分发挥出它们各自的优势，将他们的性能综合在一起，即可得到导电性能与催化性能具佳的复合涂层2和二硼化钛/碳化硼复合电极。
本申请优选实施方式中，所复合涂层2设置在所述基体1一侧表面或所述基体1相对的两侧表面。优选地，本申请的复合涂层2设置在所述基体1的相对两侧的表面，进一步地提高二硼化钛/碳化硼复合电极的催化性能。
本申请优选实施方式中，二硼化钛/碳化硼复合电极进一步包括设置在所复合涂层2表面的电极活性材料层。本申请中含有基体1的复合涂层2可充当电极中的集流体，并在复合涂层2的表面涂覆活性材料层，共同组成电极。
本申请优选实施方式中，所述基体1的材质包括钛和硅中的一种或多种。优选地，本申请中的基体1可以为钛基片、钛网或者硅片。更优选地，本申请中的基片可以为钛网。网状结构的钛网相较于现有的钛片或硅片基体1具有更大的比表面积，可提高复合涂层2与基体1之间的结合力。另外，复合涂层2 由于沉积在三维网状的钛网上，因此也提高了复合涂层2的比表面积，进一步提高了复合涂层2的活性位点，这在一定程度上又增强了二硼化钛/碳化硼复合电极的催化性能。更优选地，基体1为50-200目的钛网。
请参考图2-图3，本申请优选实施方式中，所述复合涂层2包括设置于所述基体1上的平整结构层21和设置于所述平整结构层21表面的阵列凸起22结构。与普通的平坦结构的复合涂层2相比，阵列凸起22结构的复合涂层2具有取向排列的结构优势，不仅大大提高了其比表面积，而且使更多的活性位点暴露出来，增大了其电催化还原氮气的能力，从而提高了催化效率。优选地，所述阵列凸起22垂直设置于所述平整结构层21上。
本申请优选实施方式中，所述阵列凸起22的形状为棱柱、棱锥、圆锥或针状。其中，当阵列凸起22的形状为棱柱时，如图2所示，当阵列凸起22的形状为棱锥、圆锥或针状时，如图3所示。优选地，阵列凸起22的形状为棱锥、圆锥、或针状。棱锥、圆锥、或针状的阵列凸起22的顶端(远离所述基体1的一端)为尖端。具有尖端的阵列凸起22可以起到聚集电子的作用，使电子的传输与流通更易于进行。优选地，棱锥、圆锥、或针状的阵列凸起22结构的多个凸起之间是间隔设置或紧密连接的。更优选地，棱锥、圆锥、或针状的阵列凸起22结构的多个凸起之间是紧密连接的。
本申请优选实施方式中，所述阵列凸起22的形状为棱锥、圆锥或针状；棱锥、圆锥或针状的所述阵列凸起22的顶端曲率半径为50-500nm。棱锥、圆锥或针状的顶端(如图3中阵列凸起2222远离平整结构层2121的一端)并不是一个点，而是具有一定的曲率半径，这些尖锐的纳米尖端会显著放大局部电场，从而产生电场增强效应，高的电场可能会增强电极尖端附近的试剂浓度， 实现碱金属离子富集作用，使得电极的催化效率显著提高。优选地，棱锥、圆锥或针状的所述阵列凸起22的顶端曲率半径为100-400nm。更优选地，棱锥、圆锥或针状的所述阵列凸起22的顶端曲率半径为200-300nm。
请参考图4-图5，本申请优选实施方式中，在所述复合涂层2中，所述碳化硼23的含量由靠近所述基体1的一侧至远离所述基体1的一侧逐渐增加。本申请复合涂层2中碳化硼23并不是均匀分布的，因为碳化硼23可以提高催化活性，而电极在使用过程中，应用最多的部位是电极的表面，NRR反应也是在电极表面进行的，因此碳化硼23的含量由靠近所述基体1的一侧至远离所述基体1的一侧逐渐增加不仅可以提高复合涂层2与基体1的结合力，更可以使复合涂层2表面的碳化硼23含量提高，进一步地提高了二硼化钛/碳化硼复合电极的催化活性。
本申请优选实施方式中，所述复合涂层2中所述二硼化钛的质量分数为1-50％，所述碳化硼23的质量分数为50-99％。由于二硼化钛的导电性能优异，但催化性能较差，而碳化硼23的催化性能优异，而导电性能较差。因此从上述可以发现，二硼化钛和碳化硼23是会相互影响的，二硼化钛的含量过多会降低二硼化钛/碳化硼复合电极的催化性能，而碳化硼23的含量过多会影响电极的导电性能。因此二硼化钛和碳化硼23的含量并不是简单的叠加，二硼化钛和碳化硼23是一个整体，是不可分割独立来看的。所以才需要复合涂层2中所述二硼化钛的质量分数为1-50％，所述碳化硼23的质量分数为50-99％，才能获得综合性能优异的二硼化钛/碳化硼复合电极。优选地，所述复合涂层2中所述二硼化钛的质量分数为10-40％，所述碳化硼23的质量分数为60-90％。更优选地，所述复合涂层2中所述二硼化钛的质量分数为20-30％，所述碳化 硼23的质量分数为70-80％。
本申请优选实施方式中，所述复合涂层2的厚度为600nm-6μm，所述阵列凸起22的高度为50-500nm。通过控制制备过程中的实验参数，可最终制备出600nm-6μm的复合涂层2。其中阵列凸起22的高度为50-500nm，而剩下的厚度则为平坦层的厚度。优选地，所述复合涂层2的厚度为1μm-5μm，所述阵列凸起22的高度为100-400nm。更优选地，所述复合涂层2的厚度为2μm-4μm，所述阵列凸起22的高度为200-300nm。
请参考图6，本申请实施例提供的一种二硼化钛/碳化硼复合电极的制备方法，包括：
取基体1，对所述基体1进行清洗操作，在清洗后的所述基体1上沉积复合涂层2，所述复合涂层2包括二硼化钛和碳化硼23，得到二硼化钛/碳化硼复合电极。
本申请实施例提供的制备方法，通过简单的工艺即可制备出电催化氮气还原生成氨气性能优异的二硼化钛/碳化硼复合电极，制备简单，成本低廉，在较恶劣的情况下使用寿命较高，具有很强的实用性。
本申请优选实施方式中，在清洗后的所述基体1上沉积复合涂层2，在沉积过程中，将本底真空抽至10 -3Pa，关闭离子源，角度阀调整到90，偏压调整到30-80V，将氩气流量调整到200-400sccm，将碳靶和二硼化钛靶材的靶功率设为1500-2500W，靶电流设为4.5-6A，然后打开碳靶和二硼化钛靶，镀膜10-30min。
本申请优选实施方式中，在清洗后的所述基体1上沉积复合涂层2之后，还包括在所述复合涂层2的表层进行刻蚀以形成阵列凸起22结构，使所述复 合涂层2包括设置于所述基体1上的平整结构层21和设置于所述平整结构层21表面的阵列凸起22结构，得到二硼化钛/碳化硼复合电极。本申请采用直流等离子体刻蚀技术进行刻蚀。
本申请优选实施方式中，最后进行刻蚀操作，在刻蚀过程中，将表面沉积有二硼化钛/碳化硼23复合涂层2的基体1置于热丝化学气相沉积设备中，使用直径为0.5mm的钽丝作为灯丝，并将钽丝的温度加热至1500-3000℃。将钽丝与基体1之间的间距调整为8mm，使得基体1的温度为600-1000℃。在基体1上施加200-400V的负偏压，以使用直流恒压源产生辉光放电进行刻蚀。通入的气体包括甲烷和氢气，甲烷和氢气的体积比为(1-5):(90-100)，刻蚀的压力为10-20torr，刻蚀温度为600-1000℃，刻蚀时间为2-6h，最终得到二硼化钛/碳化硼复合电极。
本申请实施例提供的二硼化钛/碳化硼复合电极在电催化还原氮气中的应用。本申请实施例利用本申请实施例提供的二硼化钛/碳化硼复合电极来电催化氮气还原氨气，催化效率、催化产量较高。另外，本申请实施例提供的二硼化钛/碳化硼复合电极还可用于电催化二氧化碳还原，氧还原，甲醇氧化等其他电化学反应，也具有很高的催化活性。
本申请实施例提供的一种用于催化氮气还原生成氨气的双电池反应器，其特征在于，包括工作电极112、对电极111和参比电极113，所述工作电极112包括如本申请实施例提供的二硼化钛/碳化硼复合电极。
请参阅图7，本申请优选实施方式中，二硼化钛/碳化硼复合电极应用于双电池反应器，其中，阳极室101和阴极室112用质子交换膜103隔离。采用三电池体系，将本申请实施例的二硼化钛/碳化硼复合电极作为工作电极112，石 墨棒为对电极111，Ag/AgCl为参比电极113。其中，工作电极112和参比电极113位于阴极室102，对电极111位于阳极室101，并与电压表114相连接，工作电极和对电极间距2-5cm。电源104分别与工作电极112，对电极111，参比电极113和电压表114相连接。在阴极室102设有一入气口115和一出气口116。入气口115用于通入氮气，出气口116用于多余氮气的排除。
下面本申请将分为多个实施例对本申请做进一步说明：
实施例1：
步骤1：将钛网分别在丙酮、无水酒精以及去离子水中清洗10min，然后在烘箱中过夜烘干。
步骤2：将钛网固定于挡板上并悬挂设置于磁控溅射设备中，保持基片平行且正对着靶材，靶材与基片表面的间距为8cm，同时设置钛网的转速为2r/min。再进行抽真空操作，在抽真空过程中，首先打开机械泵和粗抽阀，将磁控溅射设备的沉积腔室的压力抽至10Pa时打开维持阀，将沉积腔室的压力抽至4Pa，再关闭粗抽阀，打开高阀，最终将沉积腔室抽至5×10 -3Pa。
步骤3：随后进行靶材和样品的清洗操作，在清洗靶材的过程中，打开碳靶和二硼化钛靶，通入300sccm的氩气，清洗5min。在清洗样品的过程中，将氩气的流量调整到500sccm，偏压设置为800V，清洗5min。然后将角度阀调整到45，打开离子源，将氩气的流量调整到300sccm，偏压调整到150V，清洗20min。
步骤4：在清洗后的所述钛网上沉积复合涂层2，在沉积过程中，将本底真空抽至10 -3Pa，关闭离子源，角度阀调整到90，偏压调整到30V，将氩气流量 调整到200sccm，将碳靶和二硼化钛靶材的靶功率设为1500W，靶电流设为4.5A，然后打开碳靶和二硼化钛靶，镀膜10min。镀膜结束后，将钛网的另一侧正对靶材，重复步骤2到步骤4。
步骤5：最后进行刻蚀操作，在刻蚀过程中，将表面沉积有二硼化钛/碳化硼23复合涂层2的钛网置于热丝化学气相沉积设备中，使用直径为0.5mm的钽丝作为灯丝，并将钽丝的温度加热至1500℃。将钽丝与钛网之间的间距调整为8mm，使得钛网的温度为600℃。在钛网上施加200V的负偏压，以使用直流恒压源产生辉光放电进行刻蚀。通入的气体包括甲烷和氢气，甲烷和氢气的体积比为1:100，刻蚀的压力为10torr，刻蚀温度为600℃，刻蚀时间为2h，最终得到二硼化钛/碳化硼复合电极。
实施例2：
步骤1：将钛片分别在丙酮、无水酒精以及去离子水中清洗20min，然后在烘箱中过夜烘干。
步骤2：将钛片固定于挡板上并悬挂设置于磁控溅射设备中，保持基片平行且正对着靶材，靶材与基片表面的间距为20cm，同时设置钛片的转速为2r/min。再进行抽真空操作，在抽真空过程中，首先打开机械泵和粗抽阀，将磁控溅射设备的沉积腔室的压力抽至10Pa时打开维持阀，将沉积腔室的压力抽至4Pa，再关闭粗抽阀，打开高阀，最终将沉积腔室抽至6×10 -3Pa。
步骤3：随后进行靶材和样品的清洗操作，在清洗靶材的过程中，打开碳靶和二硼化钛靶，通入300sccm的氩气，清洗10min。在清洗样品的过程中，将氩气的流量调整到500sccm，偏压设置为800V，清洗10min。然后将角度阀调 整到45，打开离子源，将氩气的流量调整到300sccm，偏压调整到150V，清洗20min。
步骤4：在清洗后的所述钛片上沉积复合涂层2，在沉积过程中，将本底真空抽至10 -3Pa，关闭离子源，角度阀调整到90，偏压调整到80V，将氩气流量调整到400sccm，将碳靶和二硼化钛靶材的靶功率设为2500W，靶电流设为6A，然后打开碳靶和二硼化钛靶，镀膜30min。镀膜结束后，将钛片的另一侧正对靶材，重复步骤2到步骤4。
步骤5：最后进行刻蚀操作，在刻蚀过程中，将表面沉积有二硼化钛/碳化硼23复合涂层2的钛片置于热丝化学气相沉积设备中，使用直径为0.5mm的钽丝作为灯丝，并将钽丝的温度加热至3000℃。将钽丝与钛片之间的间距调整为8mm，使得钛片的温度为1000℃。在钛片上施加400V的负偏压，以使用直流恒压源产生辉光放电进行刻蚀。通入的气体包括甲烷和氢气，甲烷和氢气的体积比为5:90，刻蚀的压力为20torr，刻蚀温度为1000℃，刻蚀时间为6h，最终得到二硼化钛/碳化硼复合电极。
实施例3：
步骤1：将硅片分别在丙酮、无水酒精以及去离子水中清洗15min，然后在烘箱中过夜烘干。
步骤2：将硅片固定于挡板上并悬挂设置于磁控溅射设备中，保持基片平行且正对着靶材，靶材与基片表面的间距为15cm，同时设置硅片的转速为2r/min。再进行抽真空操作，在抽真空过程中，首先打开机械泵和粗抽阀，将 磁控溅射设备的沉积腔室的压力抽至10Pa时打开维持阀，将沉积腔室的压力抽至4Pa，再关闭粗抽阀，打开高阀，最终将沉积腔室抽至5.5×10 -3Pa。
步骤3：随后进行靶材和样品的清洗操作，在清洗靶材的过程中，打开碳靶和二硼化钛靶，通入300sccm的氩气，清洗10min。在清洗样品的过程中，将氩气的流量调整到500sccm，偏压设置为800V，清洗10min。然后将角度阀调整到45，打开离子源，将氩气的流量调整到300sccm，偏压调整到150V，清洗20min。
步骤4：在清洗后的所述硅片上沉积复合涂层2，在沉积过程中，将本底真空抽至10 -3Pa，关闭离子源，角度阀调整到90，偏压调整到50V，将氩气流量调整到300sccm，将碳靶和二硼化钛靶材的靶功率设为2000W，靶电流设为5.3A，然后打开碳靶和二硼化钛靶，镀膜20min。镀膜结束后，将钛网的另一侧正对靶材，重复步骤2到步骤4。
步骤5：最后进行刻蚀操作，在刻蚀过程中，将表面沉积有二硼化钛/碳化硼23复合涂层2的硅片置于热丝化学气相沉积设备中，使用直径为0.5mm的钽丝作为灯丝，并将钽丝的温度加热至2100℃。将钽丝与硅片之间的间距调整为8mm，使得硅片的温度为800℃。在硅片上施加300V的负偏压，以使用直流恒压源产生辉光放电进行刻蚀。通入的气体包括甲烷和氢气，甲烷和氢气的体积比为1.5:98，刻蚀的压力为15torr，刻蚀温度为800℃，刻蚀时间为4h，最终得到二硼化钛/碳化硼复合电极。
效果实施例
将实施例1-3得到的二硼化钛/碳化硼复合电极制成双电池反应器。采用三电极体系，将刻蚀成功的二硼化钛/碳化硼复合电极作为工作电极112，石墨棒为对电极111，Ag/AgCl为参比电极113，工作电极112和对电极111间距2cm，参比电极113靠近工作电极112。阴极室101加入饱和的0.1M的HCl溶液，阳极室112加入等体积的0.1M的HCl溶液。电催化还原N 2在-1.05～0V的恒定电压下进行，之后分别在中性以及碱性电解液中进行还原性能的测试，最后分别通过靛酚蓝方法测定氮还原产生的氨的量。测试结果如表1所示。
  法拉第效率(％) 氨产率(μg h -1mg -1) 循环次数
实施例1 14 16 7
实施例2 18 28 8
实施例3 25 36 8
表1氨气的产量
从表1中可以看出，实施例1-3中得到的二硼化钛/碳化硼复合电极的电催化氮气还原生成氨气的性能都较优异，其中实施例3得到的二硼化钛/碳化硼复合电极的电催化氮气还原生成氨气的性能最好，具有最高的法拉第效率、氨气产率和循环次数，具有很强的实用性。
以上对本申请实施方式所提供的内容进行了详细介绍，本文对本申请的原理及实施方式进行了阐述与说明，以上说明只是用于帮助理解本申请的方法及其核心思想；同时，对于本领域的一般技术人员，依据本申请的思想，在具体实施方式及应用范围上均会有改变之处，综上所述，本说明书内容不应理解为对本申请的限制。

Claims (10)

  1. 一种二硼化钛/碳化硼复合电极，其特征在于，包括基体以及设于所述基体上的复合涂层，所述复合涂层包括二硼化钛和碳化硼。
  2. 如权利要求1所述的二硼化钛/碳化硼复合电极，其特征在于，所述复合涂层包括设置于所述基体上的平整结构层和设置于所述平整结构层表面的阵列凸起结构。
  3. 如权利要求2所述的二硼化钛/碳化硼复合电极，其特征在于，所述阵列凸起的形状为棱柱、棱锥、圆锥或针状。
  4. 如权利要求2所述的二硼化钛/碳化硼复合电极，其特征在于，所述阵列凸起的形状为棱锥、圆锥或针状；棱锥、圆锥或针状的所述阵列凸起的顶端曲率半径为50-500nm。
  5. 如权利要求1或2所述的二硼化钛/碳化硼复合电极，其特征在于，在所述复合涂层中，所述碳化硼的含量由靠近所述基体的一侧至远离所述基体的一侧逐渐增加。
  6. 如权利要求1所述的二硼化钛/碳化硼复合电极，其特征在于，所述复合涂层中所述二硼化钛的质量分数为1-50％，所述碳化硼的质量分数为50-99％。
  7. 如权利要求1所述的二硼化钛/碳化硼复合电极，其特征在于，所述复合涂层的厚度为600nm-6μm，所述阵列凸起的高度为50-500nm。
  8. 一种二硼化钛/碳化硼复合电极的制备方法，其特征在于，包括：
    取基体，对所述基体进行清洗操作，在清洗后的所述基体上沉积复合涂层， 所述复合涂层包括二硼化钛和碳化硼，得到二硼化钛/碳化硼复合电极。
  9. 如权利要求8所述的制备方法，其特征在于，在清洗后的所述基体上沉积复合涂层之后，还包括在所述复合涂层的表层进行刻蚀以形成阵列凸起结构，使所述复合涂层包括设置于所述基体上的平整结构层和设置于所述平整结构层表面的阵列凸起结构，得到二硼化钛/碳化硼复合电极。
  10. 如权利要求1-7任一项所述的二硼化钛/碳化硼复合电极在电催化还原氮气中的应用。
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