CN111206271B - Preparation method, product and application of self-supporting metal doped iron nitride electrode - Google Patents
Preparation method, product and application of self-supporting metal doped iron nitride electrode Download PDFInfo
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Abstract
The invention relates to a preparation method, a product and application of a self-supporting metal doped iron nitride electrode. The purpose is to solve the technical problems of high equipment requirement, complex preparation and strict reaction conditions in the preparation process of the existing electrode. The technical scheme of the invention is as follows: firstly, iron foil is taken as an anode, a platinum sheet is taken as a cathode, and the content of NH is 0.1mol/L4F and 1mol/L H2Using ethylene glycol solution of O as electrolyte, and oxidizing the iron foil for 10-120 minutes by adopting a direct current constant voltage of 20-65V to generate porous iron oxide with iron as a conductive substrate; then carrying out electrodeposition in electrolyte containing metal salts with different concentrations to dope the metal into the porous ferric oxide. And (3) placing the metal-doped iron oxide in ammonia gas for nitridation reaction at 400-700 ℃ for 30-120 minutes to obtain the self-supporting metal-doped iron nitride film electrode. The preparation method has the advantages of simple preparation process, low cost, stable prepared electrode structure, high catalytic performance, high cycle stability and the like, and can be directly applied to the electrocatalytic oxygen evolution reaction.
Description
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to a preparation method, a product and application of a self-supporting metal doped iron nitride electrode.
Background
Global warming and environmental crisis are becoming more severe, non-renewable energy consumption is increasing, fossil fuel reserves are rapidly declining, and there is an urgent need for human beings to utilize clean, sustainable energy sources such as solar, wind, water and nuclear energy and the electrical energy generated thereby in the future. Therefore, the problem of conversion and storage of new energy is urgently solved. The electrolysis of water is considered as a technology capable of directly and efficiently producing clean energy hydrogen, and has attracted extensive attention. The water electrolysis process includes a cathodic Hydrogen Evolution Reaction (HER) and an anodic Oxygen Evolution Reaction (OER). The OER process involves four electron transfer, requires a higher overpotential, and is a bottleneck for the water splitting full reaction. At present, the noble metal oxide RuO2Or IrO2Is a common catalyst for oxygen evolution reaction, but has high price and productionThe cost is high, so that the search for high-efficiency and cheap catalyst materials has very important practical significance.
The metallic element Fe is the most abundant transition metal in the earth crust, and has been widely applied to a plurality of potential catalysts in the electrocatalysis of OER. Among them, the common iron oxides and sulfides have poor conductivity, which causes schottky energy barrier formation between the conductive substrate and the catalyst, catalyst and electrolyte, and causes large overpotential. Therefore, it is very important to develop Fe-based OER catalysts having higher conductivity. It is noted that iron nitride has metal-like properties that ensure faster electron transport and is an attractive catalyst. By reasonably designing and regulating the structure, the composition and the like of the material, such as constructing structures of nano particles, nano layers, nano wires, nano chains and the like, the specific surface area of the material can be effectively increased, the utilization rate of catalytic sites is improved, and the material is expected to replace the application and development of noble metals in electrochemical catalysis. The porous structure with high conductivity can effectively promote mass transfer of reactants and products in the electrocatalysis process, accelerate electronic conduction and enhance the wettability of the material. For the occurrence in OH-Catalyst and O2The OER reaction at the three-phase interface, and the porous, hydrophilic and gas-permeable catalyst with high wettability can effectively promote the adsorption and conduction of ions and the desorption of bubbles. However, Fe catalysts with a single metal site are too strongly adsorbed to the intermediate product OH of the OER process, resulting in the subsequent OOH, O intermediates and O on the catalyst surface2The processing of the product is extremely difficult. Therefore, the introduction of various metal sites into the iron nitride can effectively balance the adsorption and desorption binding energy of reaction intermediate species in the OER process, thereby improving the catalytic activity of the catalyst.
Throughout the literature and patents, conventional nitride catalysts are prepared by using nano iron oxide powder and the like as an iron source, reducing the iron source in a rotary kiln at least higher than 450 ℃ by using a reducing atmosphere of methanol, CO, hydrogen, hydrocarbon and the like, and then nitriding the reduced iron source (application number CN 201811411671.1). In the preparation process, reducing atmosphere gas is needed, and the reduced iron powder has high activity and serious mutual agglomeration and is easy to limit the nitriding process. In order to overcome agglomeration, a method of coating alumina and silicon oxide outside nano iron oxide powder is adopted for some researches, and a certain effect is achieved. However, the coated alumina and silica do not have catalytic activity and conductivity, and the application of the coated alumina and silica to electrocatalytic reaction will reduce the catalytic efficiency of the system. Application number CN201810338951.8 discloses a preparation method of a porous nitrogen-doped carbon-supported iron nitride catalyst, which comprises the steps of carrying out hydrothermal treatment on benzenetricarboxylic acid, reduced iron powder, nitric acid and hydrofluoric acid to obtain an iron oxide precursor, grinding and mixing the iron oxide precursor with polyaniline, and sintering the mixture to obtain the catalyst. The operation of the invention must combine the steps of hydrothermal, centrifugation, cleaning, drying and the like, the process is complicated, the requirement on equipment is high, high-temperature and high-pressure resistant steel and corrosion resistant lining are required, the temperature and pressure control is strict, and the safety performance is poor. The materials obtained in the above patents are mostly powders, and need to be grinded, mixed, coated or dripped on a conductive substrate for electrocatalytic reaction. The weaker interaction force between the active material and the conductive substrate greatly affects the stability and practicality of the electrode. Application numbers CN201610469980.9, CN201610469968.8 and CN201610469979.6 disclose iron nitride materials grown on alumina substrates, aluminum plate substrates and glass substrates, respectively, and such materials require the use of sodium hydroxide to remove the substrates, washing, filtering and drying before being used as catalysts. In addition, the research on metal doping of iron nitride is less, a common metal doping multi-purpose solvent method or a hydrothermal method (CN201610827571.1, CN201510161755.4, CN201510565389.9) reacts for 2-72 hours at the temperature of 100-240 ℃, cleaning, drying and other steps are needed, the equipment requirement is high, the process is complicated, and the time consumption is long. In conclusion, the existing production processes of iron nitride and metal-doped iron nitride have the problems of high energy consumption, complex process, poor safety performance, complex electrode preparation process and the like.
Disclosure of Invention
In order to solve the technical problems, the invention adopts the technical scheme that:
a preparation method of a self-supporting metal doped iron nitride electrode comprises the following steps:
(1) preparing self-supporting porous iron oxide: respectively using iron foilUltrasonically cleaning ketone and ethanol, removing organic matters on the surface, blow-drying with nitrogen, taking the blow-dried iron foil as an anode, taking another platinum sheet as a cathode, and adopting a solution containing 0.1mol/L NH4F and 1mol/L H2Using ethylene glycol solution of O as electrolyte, oxidizing the iron foil for 10-120 minutes by using a direct current constant voltage of 20-65V, cleaning the oxidized iron foil, and blow-drying the iron foil by using nitrogen to obtain porous iron oxide taking iron as a conductive substrate;
(2) electro-deposition of metal: taking the porous iron oxide prepared in the step (1) as a cathode and a platinum sheet as an anode, performing electrodeposition in an electrolyte containing 0.9-1.2 mol/L of metal salt, adjusting the pH of the electrolyte to 2.5 by adopting boric acid, adjusting the deposition voltage to 0.5-2.0V, and performing deposition for 5-30 minutes, cleaning the deposition product with distilled water, and drying the deposition product with nitrogen to obtain the metal-doped porous iron oxide;
(3) low-temperature nitridation: and (3) placing the metal-doped porous iron oxide prepared in the step (2) in the center of a quartz tube of a CVD tube furnace, performing nitridation reaction at the furnace temperature of 400-700 ℃, the ammonia gas flow of 50-100 sccm, the argon gas flow of 50-200 sccm and the total gas pressure of 2.5-4.5 Torr for 30-120 minutes, and rapidly cooling to room temperature to prepare the self-supporting metal-doped iron nitride electrode taking iron as the conductive substrate.
Further, the surface area ratio of the cathode to the anode in the step (1) is 1-4: 1.
Further, the metal salt in the step (2) is one or a mixture of more of nickel sulfate, nickel chloride, cobalt sulfate, cobalt nitrate, nickel nitrate and cobalt chloride in any proportion.
The self-supporting metal-doped iron nitride electrode prepared by the invention has a nanotube structure, nanotubes are regularly arranged, and metal substances are uniformly filled in the nanotubes.
The self-supporting metal doped iron nitride electrode prepared by the invention is applied to oxygen evolution reaction catalysis.
The invention has the beneficial effects that:
1. the invention adopts the anodic iron oxide film as the nitridation precursor, has higher activity, does not need reducing agent for reduction, and the obtained material is directly riveted on the iron foil substrate and is not easy to agglomerate in the nitridation process.
2. The preparation method is simple, low in cost and rich in element reserves, only needs metal iron foil, metal salt and ammonia gas as raw materials, is prepared by a simple and quick three-step method (anodic oxidation-electrodeposition-gas phase nitridation method), is in-situ and continuous in reaction process, does not need washing and drying, and reduces the process flow.
3. In the electrode prepared by the invention, the metal iron foil is used as a conductive substrate, and an iron source is also provided, so that iron nitride directly and uniformly grows on the iron foil, and the mechanical stability of the electrode structure is effectively improved;
4. compared with the traditional process, the integrated electrode prepared by the invention does not need auxiliary materials such as a conductive agent, a binder and the like in the electrode preparation process, does not need the operation processes such as grinding, slurry preparation, drying and the like when used as the OER electrode, does not need to introduce an additional conductive substrate, and has the advantages of simple and easy process, low cost and short period.
5. The electrochemical method has high selectivity in the reaction process, can adjust the relative voltage and the electrode size to meet the industrial requirement, reduces unnecessary side reaction compared with the traditional solvent method, improves the utilization rate of raw materials, increases the purity and yield of products, reduces the separation difficulty of the products, and is convenient for batch industrial production.
6. The OER catalytic performance of the self-supporting cobalt-nickel doped iron nitride electrode prepared by the invention exceeds that of commercial RuO2。
Drawings
FIG. 1 is an SEM photograph of porous iron oxide obtained after the anodic treatment in example 1 of the present invention;
FIG. 2 is a TEM image of a free-standing nickel-doped iron nitride electrode prepared in example 1 of the present invention;
FIG. 3 is a SEM image of a cross section of cobalt-nickel doped iron oxide obtained by electrodeposition in example 2 of the present invention;
FIG. 4 is a SEM image of a cross section of a free-standing cobalt-nickel doped iron nitride obtained in example 2 of the present invention;
FIG. 5 is a TEM image of a free-standing cobalt-nickel doped iron nitride obtained in example 2 of the present invention;
FIG. 6 is an XRD pattern of a free-standing cobalt nickel doped iron nitride prepared in example 2 of the present invention;
FIG. 7 is a water drop contact angle of the surface of the self-supporting cobalt-nickel doped iron nitride electrode prepared in example 2 of the present invention;
FIG. 8 is the air contact angle of the electrode surface of the free-standing cobalt-nickel doped iron nitride prepared in example 2 of the present invention;
FIG. 9 is a TEM image of a free-standing cobalt-doped iron nitride prepared in example 3 of the present invention;
FIG. 10 is an SEM image of a free-standing cobalt-nickel doped iron nitride obtained in example 4 of the present invention;
FIG. 11 is a HRTEM image of free-standing cobalt-nickel doped iron nitride obtained in example 4 of the present invention;
FIG. 12 is an XPS plot of a free standing cobalt nickel doped iron nitride obtained in example 4 of the present invention;
FIG. 13 is a photograph of a free-standing metal-doped iron nitride electrode made in accordance with the present invention;
FIG. 14 is a polarization curve of a self-supporting metal-doped iron nitride electrode prepared according to the present invention applied to a catalytic oxygen evolution reaction;
FIG. 15 is a taffy plot of a self-supporting metal-doped iron nitride electrode prepared in accordance with the present invention applied to a catalytic oxygen evolution reaction;
FIG. 16 is a polarization curve of the self-supporting metal-doped iron nitride electrode and Pt/C electrode prepared by the present invention applied to full water splitting.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
Example 1 preparation of self-supporting nickel-doped iron nitride electrode
(1) Preparing self-supporting porous iron oxide: ultrasonic cleaning 19.6 mm square iron foil with acetone and ethanol respectively, removing organic substances on the surface, blow-drying with nitrogen, using the blow-dried iron foil as an anode, taking another 19.6 mm square platinum sheet as a cathode, and adopting a platinum sheet containing 0.1mol/L NH4F and 1mol/L H2Using ethylene glycol solution of O as electrolyte, oxidizing iron foil by using 40V direct current constant voltageAfter the oxidized iron foil is cleaned, the oxidized iron foil is dried by nitrogen gas, and porous iron oxide with iron as a conductive substrate is obtained, as shown in fig. 1, a Scanning Electron Microscope (SEM) picture of the porous iron oxide shows, and it can be seen that the iron oxide generated on the surface of the metal iron foil after anodic oxidation is in a regular porous distribution shape;
(2) electrodeposition of nickel metal: taking the porous iron oxide prepared in the step (1) as a cathode and a platinum sheet as an anode, carrying out electrodeposition in electrolyte containing 1.2mol/L nickel sulfate, adjusting the pH of the electrolyte to 2.5 by adopting boric acid, wherein the deposition voltage is 0.5V, the deposition time is 30 minutes, cleaning a deposition product by using distilled water, and drying by using nitrogen to obtain the porous iron oxide doped with nickel metal;
(3) low-temperature nitridation: placing the nickel metal doped porous iron oxide prepared in the step (2) in the center of a quartz tube of a CVD tube furnace, performing nitridation reaction at the furnace temperature of 700 ℃, the ammonia gas flow rate of 100sccm, the argon gas flow rate of 200sccm and the total gas pressure of 4.5Torr for 30 minutes, and rapidly cooling to room temperature to prepare the self-supporting nickel doped iron nitride electrode (Ni/epsilon-Fe) with iron as a conductive substrate3N). FIG. 2 shows the Ni/ε -Fe3And a TEM image of the N electrode shows that the nitrided electrode is of a nanotube structure.
Example 2 preparation of self-supporting cobalt-nickel doped iron nitride electrode
(1) Preparing self-supporting porous iron oxide: ultrasonic cleaning 19.6 square mm iron foil with acetone and ethanol respectively, removing organic substances on the surface, blow-drying with nitrogen, using the blow-dried iron foil as an anode, taking a 39.2 square mm platinum sheet as a cathode, and adopting a platinum sheet containing 0.1mol/L NH4F and 1mol/L H2Using ethylene glycol solution of O as electrolyte, oxidizing the iron foil for 120 minutes by using a 20V direct current constant voltage, cleaning the oxidized iron foil, and drying the iron foil by using nitrogen to obtain porous iron oxide taking iron as a conductive substrate;
(2) electro-deposition of cobalt-nickel metal: taking the porous ferric oxide prepared in the step (1) as a cathode, taking a platinum sheet as an anode, carrying out electrodeposition in electrolyte containing 0.45mol/L nickel sulfate, 0.19mol/L nickel chloride and 0.48mol/L cobalt sulfate, adjusting the pH of the electrolyte to 2.5 by adopting boric acid, wherein the deposition voltage is 2V, the deposition time is 10 minutes, cleaning a deposition product by using distilled water, and blowing nitrogen to dry to obtain the porous ferric oxide doped with cobalt-nickel metal; FIG. 3 is a SEM image of a cross section of the porous iron oxide film doped with Co-Ni metal, showing that nanotube arrays on the surface of the iron foil are connected to form a nanoporous film;
(3) low-temperature nitridation: placing the cobalt-nickel metal doped porous iron oxide prepared in the step (2) in the center of a quartz tube of a CVD tube furnace, performing nitridation reaction at the furnace temperature of 400 ℃, the ammonia gas flow rate of 50sccm, the argon gas flow rate of 100sccm and the total gas pressure of 2.5Torr for 90 minutes, and rapidly cooling to room temperature to obtain the self-supporting cobalt-nickel doped iron nitride electrode (CoNi/epsilon-Fe) with iron as a conductive substrate3N)。
As shown in FIG. 4 and FIG. 5, the CoNi/. epsilon. -Fe3In the SEM and TEM images of the cross section of the N electrode, it can be seen from fig. 4 and 5 that the nanotubes after nitridation are regularly arranged, and the cobalt-nickel material is uniformly filled in the nanotubes.
As shown in FIG. 6, XRD showed CoNi/ε -Fe3N is composed of epsilon-Fe3N and Co (Ni) Fe2O.
The self-supporting CoNi/epsilon-Fe prepared in the example was measured by the sitting drop method3As can be seen from fig. 7, the contact angle of the water droplet on the surface of the N electrode is 9.8 °; measurement of self-supporting CoNi/epsilon-Fe prepared in this example by bubble Capture3As can be seen from FIG. 8, the air contact angle of the N electrode was 152.3 degrees, indicating that the self-supporting CoNi/ε -Fe obtained in this example3The N electrode has a hydrophilic, gas-permeable surface.
Example 3 preparation of self-supporting cobalt-doped iron nitride electrode
(1) Preparing self-supporting porous iron oxide: ultrasonic cleaning 7 mm square iron foil with acetone and ethanol respectively, removing organic substances on the surface, blow-drying with nitrogen gas, using the blow-dried iron foil as anode, taking another 21 mm square platinum sheet as cathode, and using a platinum sheet containing 0.1mol/L NH4F and 1mol/L H2Using ethylene glycol solution of O as electrolyte, oxidizing iron foil 1 by using 65V direct current constant voltageAfter 0 minute, cleaning the oxidized iron foil, and drying the iron foil by using nitrogen to obtain porous iron oxide taking iron as a conductive substrate;
(2) electrodeposition of cobalt metal: taking the porous ferric oxide prepared in the step (1) as a cathode and a platinum sheet as an anode, carrying out electrodeposition in electrolyte containing 0.96mol/L cobalt nitrate, adjusting the pH of the electrolyte to 2.5 by adopting boric acid, wherein the deposition voltage is 1.5V, the deposition time is 15 minutes, cleaning a deposition product by using distilled water, and drying by using nitrogen to obtain the porous ferric oxide doped with cobalt metal;
(3) low-temperature nitridation: placing the cobalt metal doped porous iron oxide prepared in the step (2) in the center of a quartz tube of a CVD tube furnace, performing nitridation reaction at the furnace temperature of 500 ℃, the ammonia gas flow rate of 80sccm, the argon gas flow rate of 150sccm and the total gas pressure of 3Torr for 120 minutes, and rapidly cooling to room temperature to obtain the self-supporting cobalt doped iron nitride electrode (Co/epsilon-Fe) with iron as a conductive substrate3N). FIG. 9 shows the resulting self-supporting Co/. epsilon. -Fe3TEM images of N electrodes.
Example 4 preparation of self-supporting cobalt-nickel doped iron nitride electrode
(1) Preparing self-supporting porous iron oxide: ultrasonically cleaning 254 mm square iron foil with acetone and ethanol respectively, removing organic substances on the surface, blow-drying with nitrogen, using the blow-dried iron foil as an anode, taking another platinum sheet with 1016 mm square as a cathode, and using a platinum sheet containing 0.1mol/L NH4F and 1mol/L H2Using ethylene glycol solution of O as electrolyte, oxidizing the iron foil for 40 minutes by using 40V direct current constant voltage, cleaning the oxidized iron foil, and drying the iron foil by using nitrogen to obtain porous iron oxide taking iron as a conductive substrate;
(2) electro-deposition of cobalt-nickel metal: taking the porous iron oxide prepared in the step (1) as a cathode, taking a platinum sheet as an anode, carrying out electrodeposition in electrolyte containing 0.45mol/L nickel sulfate, 0.19mol/L nickel chloride and 0.48mol/L cobalt sulfate, adjusting the pH of the electrolyte to 2.5 by adopting boric acid, adjusting the deposition voltage to 2.0V and the deposition time to 10 minutes, cleaning the deposition product by using distilled water, and blowing nitrogen to dry to obtain the porous iron oxide doped with cobalt-nickel metal;
(3) low-temperature nitridation: placing the cobalt-nickel metal doped porous iron oxide prepared in the step (2) in the center of a quartz tube of a CVD tube furnace, performing nitridation reaction at the furnace temperature of 400 ℃, the ammonia gas flow rate of 100sccm, the argon gas flow rate of 200sccm and the total gas pressure of 3Torr for 60 minutes, rapidly cooling to room temperature to prepare the self-supporting cobalt-nickel doped iron nitride electrode with iron as a conductive substrate,
fig. 10 and 11 are SEM and HRTEM images of the free-standing cobalt-nickel doped iron nitride electrode prepared in this example, respectively. In FIG. 11
Lattice spacing and 60 DEG included angle of crystal face corresponding to Fe3The (210) and (110) crystal planes of N. FIG. 12 is an XPS map of the electrode, the electrode surface consisting of Fe, Co, Ni, O, C, N elements.
Example 5 preparation of self-supporting cobalt-doped iron nitride electrode
(1) Preparing self-supporting porous iron oxide: ultrasonically cleaning 254 mm square iron foil with acetone and ethanol respectively, removing organic substances on the surface, blow-drying with nitrogen, taking the blow-dried iron foil as an anode, taking another 254 mm square platinum sheet as a cathode, and adopting a solution containing 0.1mol/L NH4F and 1mol/L H2Using ethylene glycol solution of O as electrolyte, oxidizing the iron foil for 40 minutes by using 40V direct current constant voltage, cleaning the oxidized iron foil, and drying the iron foil by using nitrogen to obtain porous iron oxide taking iron as a conductive substrate;
(2) electrodeposition of cobalt metal: taking the porous ferric oxide prepared in the step (1) as a cathode and a platinum sheet as an anode, carrying out electrodeposition in electrolyte containing 0.9mol/L cobalt chloride, adjusting the pH of the electrolyte to 2.5 by adopting boric acid, wherein the deposition voltage is 2.0V, the deposition time is 5 minutes, cleaning a deposition product by using distilled water, and drying by using nitrogen to obtain the porous ferric oxide doped with cobalt metal;
(3) low-temperature nitridation: and (3) placing the cobalt metal doped porous iron oxide prepared in the step (2) in the center of a quartz tube of a CVD tube furnace, performing nitridation reaction at the furnace temperature of 400 ℃, the ammonia gas flow rate of 100sccm, the argon gas flow rate of 200sccm and the total gas pressure of 3Torr for 60 minutes, and rapidly cooling to room temperature to obtain the self-supporting cobalt doped iron nitride electrode taking iron as a conductive substrate.
Example 6 preparation of self-supporting nickel-doped iron nitride electrode
(1) Preparing self-supporting porous iron oxide: ultrasonic cleaning 19.6 square mm iron foil with acetone and ethanol respectively, removing organic substances on the surface, blow-drying with nitrogen, using the blow-dried iron foil as an anode, taking a 25 square mm platinum sheet as a cathode, and using a platinum sheet containing 0.1mol/L NH4F and 1mol/L H2Using ethylene glycol solution of O as electrolyte, oxidizing the iron foil for 60 minutes by using 30V direct current constant voltage, cleaning the oxidized iron foil, and drying the iron foil by using nitrogen to obtain porous iron oxide taking iron as a conductive substrate;
(2) electrodeposition of nickel metal: taking the porous iron oxide prepared in the step (1) as a cathode and a platinum sheet as an anode, carrying out electrodeposition in electrolyte containing 1.0mol/L nickel nitrate, adjusting the pH of the electrolyte to 2.5 by adopting boric acid, wherein the deposition voltage is 2.0V, the deposition time is 20 minutes, cleaning a deposition product by using distilled water, and drying by using nitrogen to obtain the porous iron oxide doped with nickel metal;
(3) low-temperature nitridation: and (3) placing the nickel metal doped porous iron oxide prepared in the step (2) in the center of a quartz tube of a CVD tube furnace, performing nitridation reaction at the furnace temperature of 400 ℃, the ammonia gas flow of 100sccm, the argon gas flow of 50sccm and the total gas pressure of 3Torr for 60 minutes, and rapidly cooling to room temperature to prepare the self-supporting nickel doped iron nitride electrode taking iron as a conductive substrate.
As shown in fig. 13, the photographs of the self-supporting metal-doped iron nitride electrodes obtained in example 2 (left 1), example 1 (middle), and example 4 (right 1), respectively. Therefore, the preparation method is suitable for preparing catalysts with different areas, and is beneficial to industrial production and application.
Application examples
The application of the self-supporting metal doped iron nitride electrode prepared by the invention in electrocatalysis oxygen evolution reaction is as follows:
the self-prepared by the invention is applied to an electrochemical workstation of CHI-760E model of Shanghai ChenghuaAnd testing the oxygen evolution catalysis performance of the support metal doped iron nitride electrode. A1 mol/L KOH aqueous solution is used as an electrolyte, a high-purity platinum wire is used as a counter electrode, a mercury/mercury oxide electrode is used as a reference electrode, a self-supporting electrode is used as a working electrode, pure oxygen is bubbled for 30 minutes to remove dissolved oxygen, and polarization curve measurement is carried out at a sweep rate of 5 mV/s. FIGS. 14 and 15 are OER polarization curves and Tafel curves at a current density of 10mA/cm2While, CoNi/e-Fe3The oxygen evolution potential of N is 285 mV; the Tafel slope was 34.0 mV/dec. As shown in FIG. 16, when a self-supporting cobalt-nickel doped iron nitride electrode as an anode and a commercial HER catalyst Pt/C as a cathode are used together to catalyze electrolysis of water, CoNi/e-Fe3N (+) | | Pt/C (-), 10mA/cm is generated at 1.59V2Current density far exceeding RuO2(+)||Pt/C(–)。
Claims (4)
1. A preparation method of a self-supporting metal doped iron nitride electrode is characterized by comprising the following steps:
(1) preparing self-supporting porous iron oxide: ultrasonic cleaning iron foil with acetone and ethanol respectively, removing organic substances on the surface, blow-drying with nitrogen, using the blow-dried iron foil as an anode, taking another platinum sheet as a cathode, and adopting a solution containing 0.1mol/L NH4F and 1mol/L H2Using ethylene glycol solution of O as electrolyte, oxidizing the iron foil for 10-120 minutes by using a direct current constant voltage of 20-65V, cleaning the oxidized iron foil, and blow-drying the iron foil by using nitrogen to obtain porous iron oxide taking iron as a conductive substrate;
(2) electro-deposition of metal: taking the porous iron oxide prepared in the step (1) as a cathode and a platinum sheet as an anode, performing electrodeposition in an electrolyte containing 0.9-1.2 mol/L of metal salt, adjusting the pH of the electrolyte to 2.5 by adopting boric acid, adjusting the deposition voltage to 0.5-2.0V, and performing deposition for 5-30 minutes, cleaning the deposition product with distilled water, and drying the deposition product with nitrogen to obtain the metal-doped porous iron oxide;
(3) low-temperature nitridation: placing the metal-doped porous iron oxide prepared in the step (2) in the center of a quartz tube of a CVD tube furnace at the furnace temperature of 400-700 DEG CoC. The flow rate of ammonia gas is 50-100 sccm, the flow rate of argon gas is 50-200 sccm, and the totalCarrying out nitridation reaction under the air pressure of 2.5-4.5 Torr for 30-120 minutes, and rapidly cooling to room temperature to obtain the self-supporting metal doped iron nitride electrode taking iron as the conductive substrate;
the metal salt in the step (2) is one or a mixture of more of nickel sulfate, nickel chloride, cobalt sulfate, cobalt nitrate, nickel nitrate and cobalt chloride in any proportion.
2. The method of claim 1, wherein the step of forming the self-supporting metal-doped iron nitride electrode comprises: the surface area ratio of the cathode to the anode in the step (1) is 1-4: 1.
3. The self-supporting metal-doped iron nitride electrode prepared by the preparation method of the self-supporting metal-doped iron nitride electrode according to claim 1, wherein the self-supporting metal-doped iron nitride electrode is prepared by the following steps: the iron nitride electrode is of a nanotube structure, nanotubes are regularly arranged, and metal substances are uniformly filled in the nanotubes.
4. The use of the self-supporting metal-doped iron nitride electrode prepared by the method of claim 1 in oxygen evolution reaction catalysis.
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