CN113073336B - RuO2Foamed nickel composite electrode and preparation method and application thereof - Google Patents

RuO2Foamed nickel composite electrode and preparation method and application thereof Download PDF

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CN113073336B
CN113073336B CN202110326055.1A CN202110326055A CN113073336B CN 113073336 B CN113073336 B CN 113073336B CN 202110326055 A CN202110326055 A CN 202110326055A CN 113073336 B CN113073336 B CN 113073336B
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ruo
foamed nickel
composite electrode
electrode
nickel
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CN113073336A (en
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王建国
季文凯
包志康
张世杰
丁磊
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Zhejiang University of Technology ZJUT
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention discloses a RuO2The invention relates to a foamed nickel composite electrode, a preparation method and application thereof, and RuO is used as the composite electrode2As active ingredient, RuO2RuO loaded on foamed nickel carrier per square centimeter of foamed nickel2The content is between 0.19mg and 0.57 mg. The composite electrode is used as a working electrode for electrolyzing deuterium gas to prepare deuterium gas, and the electrolysis process is mainly a typical three-electrode system heavy water electrolysis process. The electrolytic process of the invention is simple and efficient, pure deuterium gas can be rapidly generated, the preparation of the composite electrode is completed in one step, and the prepared composite electrode has good stability.

Description

RuO2Foamed nickel composite electrode and preparation method and application thereof
Technical Field
The invention belongs to the technical field of material preparation and application, and particularly relates to RuO2A foamed nickel composite electrode and a preparation method and application thereof.
Background
Deuterium is an isotope of hydrogen, has the chemical symbol of D or 2H, is a colorless and odorless combustible gas at normal temperature, has the abundance of 0.015 percent on the earth, has little content in common hydrogen, and is mostly heavy water D2O, i.e. the form of deuterium oxide, is present in seawater and normal water. Deuterium, an isotope of hydrogen, also known as deuterium, consists of a proton, a neutron and an electron, and is found in liquid hydrogen in 1931 in U.S. h.c. euchryse and f.g. brikword. The mass concentration of deuterium in seawater is about 30 mg/L. Deuterium, as an isotope of hydrogen, has found wide application in military, nuclear power and optical fiber manufacturing.
The existing deuterium gas preparation technology mainly comprises liquid hydrogen rectification technology, electrolytic heavy water technology, metal hydride technology, laser technology, gas chromatography technology and the like, wherein the electrolytic heavy water technology adopts an electrolytic water device, and deuterium oxide of alkali metal is used as electrolyte or solid polymer to electrolyze heavy water. The key point of purification is to remove impurities and reduce hydrogen isotopes contained in deuterium, namely impurity protium, but the removal difficulty of protium is larger and the processing technology is very complicated. In order to improve the technology of electrolyzing the heavy water, the traditional method for directly electrolyzing the heavy water by using an electrochemical three-electrode system is adopted, the method can effectively improve the impurity removing process of the electrolyzed heavy water, and the generated gas is completely deuterium gas and has no protium.
But the energy consumption problem in the process of directly electrolyzing heavy water by an electrochemical three-electrode system is also very obvious, the working voltage is reduced and the energy efficiency is improved in the application, and the adopted working electrode plays a crucial role, so that the overpotential is reduced, the reaction process of producing deuterium is accelerated, and deuterium gas with high purity can be mildly and massively produced in an energy-saving mode. The main strategies for improving the electrolysis equipment are as follows: reducing the inter-electrode distance, increasing the working pressure, increasing the working temperature, changing the electrode material, using additives, etc. In general, the electrochemical direct electrolysis of deuterium by deuterium production from deuterium water has two problems of electrolysis and working electrode, and the key point is to solve the problem of preparing a high-efficiency durable deuterium-producing working electrode.
Disclosure of Invention
In view of the above technical problems in the prior art, the present invention aims to provide a RuO2Foamed nickel composite electrode, preparation method and application thereof, RuO of the invention2The foam nickel composite electrode has the characteristics of greenness, low price and high-efficiency catalysis, and has a wide application prospect in industrial deuterium preparation.
One kind of RuO2A composite electrode of foamed nickel, characterized in that the composite electrode is RuO2As active ingredient, RuO2RuO loaded on foamed nickel carrier per square centimeter of foamed nickel2The content is 0.19mg-0.57 mg.
One kind of RuO2Foamed nickel compositeThe preparation method of the electrode is characterized by comprising the following steps:
1) adding a ruthenium precursor into n-butanol, and uniformly dispersing by ultrasonic to obtain a ruthenium precursor-n-butanol solution for later use; soaking the foamed nickel in dilute hydrochloric acid with the concentration of 0.5wt.% for 10min, taking out the foamed nickel, washing the residual hydrochloric acid on the surface of the foamed nickel by using water, and drying to obtain the cleaned foamed nickel for later use;
2) dripping the ruthenium precursor-n-butyl alcohol solution obtained in the step 1) on the cleaned foam nickel, and then calcining at high temperature in a muffle furnace in an air environment; naturally cooling to room temperature after calcination is finished, thus obtaining the RuO2Foamed nickel composite electrodes.
One kind of RuO2The preparation method of the foamed nickel composite electrode is characterized in that in the step 1), the ruthenium precursor is ruthenium chloride, the ratio of the mass of the ruthenium precursor to the volume of n-butanol is 20-40:1, preferably 30:1, the unit of mass is mg, and the unit of volume is mL.
One kind of RuO2The preparation method of the foamed nickel composite electrode is characterized in that when the ruthenium precursor-n-butyl alcohol solution in the step 2) is dripped on the foamed nickel, the volume of the ruthenium precursor-n-butyl alcohol solution dripped on the foamed nickel per square centimeter is 10 mu L-30 mu L, preferably 20 mu L.
One kind of RuO2The preparation method of the foamed nickel composite electrode is characterized in that in the step 2), the high-temperature calcination process in a muffle furnace comprises the following steps: under the air environment, uniformly heating from room temperature to 350-550 ℃ at the speed of 2-7 ℃/min, keeping the constant temperature for 15-60 min, and then naturally cooling to room temperature.
One kind of RuO2The preparation method of the foamed nickel composite electrode is characterized in that the high-temperature calcination process in a muffle furnace comprises the following steps: under the air environment, the temperature is uniformly raised to 450 ℃ from the room temperature at the speed of 5 ℃/min, then the temperature is kept for 30min, and then the temperature is naturally cooled to the room temperature.
The RuO2The foamed nickel composite electrode is applied to the preparation of deuterium gas by electrolyzing heavy water.
The RuO2Foamed nickelThe application of the composite electrode in the preparation of deuterium gas by electrolyzing heavy water is characterized in that the electrolysis process is carried out in a single-tank electrolytic cell, a three-electrode electrolysis system is adopted, and the RuO is adopted2The foamed nickel composite electrode is used as a working electrode, a platinum wire is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode, so that the reaction of preparing deuterium gas by electrolyzing heavy water is carried out.
Compared with the traditional electrode, the composite electrode prepared by the technology has the following advantages:
RuO prepared by the invention2The foamed nickel composite electrode takes ruthenium chloride as a precursor, and the synthesis and loading of active components are directly carried out at high temperature, so that the composite electrode with high activity for preparing deuterium gas by electrolyzing deuterium water is prepared by a one-step method, and the further exploration of the industrial application of the composite electrode is facilitated.
RuO for preparing deuterium gas by electrolyzing heavy water prepared by the invention2Compared with the traditional electrode, the foam nickel composite electrode has the advantages of less noble metal consumption, low price, good mechanical strength and good circulation stability. The catalyst has better activity when being used for preparing deuterium by electrochemically electrolyzing deuterium, and the generated gas is deuterium gas without other dopants.
RuO for preparing deuterium gas by electrolyzing heavy water prepared by the invention2The foamed nickel composite electrode is applied to deuterium making industry for the first time, is a conventional electrochemical water electrolysis method, and is beneficial to replacing the existing alkali metal deuterium oxide method to prepare deuterium gas.
Drawings
FIG. 1 shows RuO obtained in example 2 of the present invention2SEM image of the foam nickel composite electrode before reaction of preparing deuterium by electrolyzing water.
FIG. 2 shows RuO obtained in example 2 of the present invention2SEM image of the foam nickel composite electrode after water electrolysis deuterium preparation reaction.
FIG. 3 shows RuO prepared in examples 1 to 5 of the present invention2A performance test chart of the foam nickel composite electrode in the application of preparing deuterium by electrolyzing deuterium;
FIG. 4 shows RuO prepared in examples 6 to 10 of the present invention2A performance test chart of the foam nickel composite electrode in the application of preparing deuterium by electrolyzing deuterium;
FIG. 5 shows the present inventionRuO prepared in Ming examples 1, 11 to 132A performance test chart of the foam nickel composite electrode in the application of preparing deuterium by electrolyzing deuterium;
FIG. 6 shows RuO obtained in example 1 of the present invention2A life test chart of the foam nickel composite electrode in the application of preparing deuterium by electrolyzing deuterium.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1:
RuO2The preparation of the foamed nickel composite electrode (ruthenium oxide content is 0.19 mg) comprises the following steps:
1) accurately weighing 30mg of ruthenium chloride, adding the ruthenium chloride into 1ml of n-butyl alcohol, and then carrying out ultrasonic treatment for 10 minutes to fully dissolve the ruthenium chloride and the n-butyl alcohol to obtain a ruthenium chloride-n-butyl alcohol solution for later use; soaking the foamed nickel in dilute hydrochloric acid with the concentration of 0.5% for 10min, taking out the foamed nickel, washing the residual hydrochloric acid on the surface of the foamed nickel by using water, and drying to obtain the cleaned foamed nickel for later use;
2) taking 10 mu L of the ruthenium chloride-n-butyl alcohol solution obtained in the step 1) by using a pipette gun, dripping the solution on clean 1x1 square centimeter of foamed nickel, and then calcining the solution at high temperature in a muffle furnace in an air environment, wherein the process comprises the following steps: under the air environment, uniformly heating from room temperature to 450 ℃ at the speed of 5 ℃/min, keeping the constant temperature for 30min, and naturally cooling to room temperature to obtain RuO2Foamed nickel composite electrode (RuO)2The ruthenium oxide content in the nickel foam composite electrode was 0.19 mg).
Example 2:
RuO2The preparation of the foamed nickel composite electrode (ruthenium oxide content is 0.38 mg) comprises the following steps:
1) accurately weighing 30mg of ruthenium chloride, adding the ruthenium chloride into 1ml of n-butyl alcohol, and then carrying out ultrasonic treatment for 10 minutes to fully dissolve the ruthenium chloride and the n-butyl alcohol to obtain a ruthenium chloride-n-butyl alcohol solution for later use; soaking the foamed nickel in dilute hydrochloric acid with the concentration of 0.5% for 10min, taking out the foamed nickel, washing the residual hydrochloric acid on the surface of the foamed nickel by using water, and drying to obtain the cleaned foamed nickel for later use;
2) taking 20 mu with a pipetteL, dripping the ruthenium chloride-n-butyl alcohol solution obtained in the step 1) on cleaned 1x1 square centimeter foamed nickel, and then calcining at high temperature in a muffle furnace in an air environment, wherein the process comprises the following steps: under the air environment, uniformly heating from room temperature to 450 ℃ at the speed of 5 ℃/min, keeping the constant temperature for 30min, and naturally cooling to room temperature to obtain RuO2Foamed nickel composite electrode (RuO)2The ruthenium oxide content in the nickel foam composite electrode was 0.38 mg).
RuO obtained in example 2 of the invention2An SEM image of the nickel foam composite electrode is shown in fig. 1.
Example 3:
RuO2The preparation of the foamed nickel composite electrode (ruthenium oxide content is 0.57 mg) comprises the following steps:
1) accurately weighing 30mg of ruthenium chloride, adding the ruthenium chloride into 1ml of n-butyl alcohol, and then carrying out ultrasonic treatment for 10 minutes to fully dissolve the ruthenium chloride and the n-butyl alcohol to obtain a ruthenium chloride-n-butyl alcohol solution for later use; soaking the foamed nickel in dilute hydrochloric acid with the concentration of 0.5% for 10min, taking out the foamed nickel, washing the foamed nickel with residual hydrochloric acid on the surface of the foamed nickel by using water, and drying to obtain clean foamed nickel for later use;
2) using a liquid transfer gun to drop 30 mu L of the ruthenium chloride-n-butyl alcohol obtained in the step 1) on cleaned 1x1 square centimeter of foamed nickel, and then calcining the solution at high temperature in a muffle furnace in an air environment, wherein the process comprises the following steps: under the air environment, uniformly heating from room temperature to 450 ℃ at the speed of 5 ℃/min, keeping the constant temperature for 30min, and naturally cooling to room temperature to obtain RuO2Foamed nickel composite electrode (RuO)2The ruthenium oxide content in the nickel foam composite electrode was 0.57 mg).
Example 4:
RuO2The preparation of the foamed nickel composite electrode (ruthenium oxide content is 0.38 mg) comprises the following steps:
1) accurately weighing 30mg of ruthenium chloride, adding the ruthenium chloride into 1ml of n-butyl alcohol, and then carrying out ultrasonic treatment for 10 minutes to fully dissolve the ruthenium chloride and the n-butyl alcohol to obtain a ruthenium chloride-n-butyl alcohol solution for later use; soaking the foamed nickel in dilute hydrochloric acid with the concentration of 0.5% for 10min, taking out the foamed nickel, washing the residual hydrochloric acid on the surface of the foamed nickel by using water, and drying to obtain the cleaned foamed nickel for later use;
2) taking 20 mu L of the ruthenium chloride-n-butyl alcohol solution obtained in the step 1) by using a liquid transfer gun, dripping the solution on clean 1x1 square centimeter of foamed nickel, and then calcining the solution at high temperature in a muffle furnace in an air environment, wherein the process comprises the following steps: under the air environment, uniformly heating from room temperature to 350 ℃ at the speed of 5 ℃/min, keeping the constant temperature for 30min, and naturally cooling to room temperature to obtain RuO2Foamed nickel composite electrode (RuO)2The ruthenium oxide content in the nickel foam composite electrode was 0.38 mg).
Example 5:
RuO (RuO)2The preparation of the foamed nickel composite electrode (ruthenium oxide content is 0.38 mg) comprises the following steps:
1) accurately weighing 30mg of ruthenium chloride, adding the ruthenium chloride into 1ml of n-butyl alcohol, and then carrying out ultrasonic treatment for 10 minutes to fully dissolve the ruthenium chloride and the n-butyl alcohol to obtain a ruthenium chloride-n-butyl alcohol solution for later use; soaking the foamed nickel in dilute hydrochloric acid with the concentration of 0.5% for 10min, taking out the foamed nickel, washing the residual hydrochloric acid on the surface of the foamed nickel by using water, and drying to obtain the cleaned foamed nickel for later use;
2) taking 20 mu L of the ruthenium chloride-n-butyl alcohol solution obtained in the step 1) by using a liquid transfer gun, dripping the solution on clean 1x1 square centimeter of foamed nickel, and then calcining the solution at high temperature in a muffle furnace in an air environment, wherein the process comprises the following steps: under the air environment, uniformly heating from room temperature to 550 ℃ at the speed of 5 ℃/min, keeping the constant temperature for 30min, and naturally cooling to room temperature to obtain RuO2Foamed nickel composite electrode (RuO)2The ruthenium oxide content in the nickel foam composite electrode was 0.38 mg).
Example 6:
RuO2The preparation of the foamed nickel composite electrode (ruthenium oxide content is 0.38 mg) comprises the following steps:
1) accurately weighing 30mg of ruthenium chloride, adding the ruthenium chloride into 1ml of n-butyl alcohol, and then carrying out ultrasonic treatment for 10 minutes to fully dissolve the ruthenium chloride and the n-butyl alcohol to obtain a ruthenium chloride-n-butyl alcohol solution for later use; soaking the foamed nickel in dilute hydrochloric acid with the concentration of 0.5% for 10min, taking out the foamed nickel, washing the residual hydrochloric acid on the surface of the foamed nickel by using water, and drying to obtain the cleaned foamed nickel for later use;
2) taking 20 mu L of the ruthenium chloride-n-butyl alcohol solution obtained in the step 1) by using a liquid transfer gun, dripping the solution on clean 1x1 square centimeter of foamed nickel, and then calcining the solution at high temperature in a muffle furnace in an air environment, wherein the process comprises the following steps: under the air environment, uniformly heating from room temperature to 450 ℃ at the speed of 5 ℃/min, keeping the constant temperature for 15min, and naturally cooling to room temperature to obtain RuO2Foamed nickel composite electrode (RuO)2The ruthenium oxide content in the nickel foam composite electrode was 0.38 mg).
Example 7:
RuO2The preparation of the foamed nickel composite electrode (ruthenium oxide content is 0.38 mg) comprises the following steps:
1) accurately weighing 30mg of ruthenium chloride, adding the ruthenium chloride into 1ml of n-butyl alcohol, and then carrying out ultrasonic treatment for 10 minutes to fully dissolve the ruthenium chloride and the n-butyl alcohol to obtain a ruthenium chloride-n-butyl alcohol solution for later use; soaking the foamed nickel in dilute hydrochloric acid with the concentration of 0.5% for 10min, taking out the foamed nickel, washing the residual hydrochloric acid on the surface of the foamed nickel by using water, and drying to obtain the cleaned foamed nickel for later use;
2) taking 20 mu L of the ruthenium chloride-n-butyl alcohol solution obtained in the step 1) by using a liquid transfer gun, dripping the solution on clean 1x1 square centimeter of foamed nickel, and then calcining the solution at high temperature in a muffle furnace in an air environment, wherein the process comprises the following steps: under the air environment, uniformly heating from room temperature to 450 ℃ at the speed of 5 ℃/min, keeping the constant temperature for 45min, and naturally cooling to room temperature to obtain RuO2Foamed nickel composite electrode (RuO)2The ruthenium oxide content in the nickel foam composite electrode was 0.38 mg).
Example 8:
RuO2The preparation of the foamed nickel composite electrode (ruthenium oxide content is 0.38 mg) comprises the following steps:
1) accurately weighing 30mg of ruthenium chloride, adding the ruthenium chloride into 1ml of n-butyl alcohol, and then carrying out ultrasonic treatment for 10 minutes to fully dissolve the ruthenium chloride and the n-butyl alcohol to obtain a ruthenium chloride-n-butyl alcohol solution for later use; soaking the foamed nickel in dilute hydrochloric acid with the concentration of 0.5% for 10min, taking out the foamed nickel, washing the residual hydrochloric acid on the surface of the foamed nickel by using water, and drying to obtain the cleaned foamed nickel for later use;
2) taking 20 mu L of chlorination obtained in step 1) by using a pipetteDrop coating of ruthenium-n-butanol solution on cleaned 1 × 1cm square foam nickel, and then high-temperature calcination in a muffle furnace in an air environment, wherein the process comprises the following steps: under the air environment, uniformly heating from room temperature to 450 ℃ at the speed of 5 ℃/min, keeping the constant temperature for 60min, and naturally cooling to room temperature to obtain RuO2Foamed nickel composite electrode (RuO)2The ruthenium oxide content in the nickel foam composite electrode was 0.38 mg).
Example 9:
RuO2The preparation of the foamed nickel composite electrode (ruthenium oxide content is 0.38 mg) comprises the following steps:
1) accurately weighing 30mg of ruthenium chloride, adding the ruthenium chloride into 1ml of n-butyl alcohol, and then carrying out ultrasonic treatment for 10 minutes to fully dissolve the ruthenium chloride and the n-butyl alcohol to obtain a ruthenium chloride-n-butyl alcohol solution for later use; soaking the foamed nickel in dilute hydrochloric acid with the concentration of 0.5% for 10min, taking out the foamed nickel, washing the residual hydrochloric acid on the surface of the foamed nickel by using water, and drying to obtain the cleaned foamed nickel for later use;
2) taking 20 mu L of the ruthenium chloride-n-butyl alcohol solution obtained in the step 1) by using a liquid transfer gun, dripping the solution on clean 1x1 square centimeter of foamed nickel, and then calcining the solution at high temperature in a muffle furnace in an air environment, wherein the process comprises the following steps: under the air environment, uniformly heating from room temperature to 450 ℃ at the speed of 3 ℃/min, keeping the constant temperature for 30min, and naturally cooling to room temperature to obtain RuO2Foamed nickel composite electrode (RuO)2The ruthenium oxide content in the nickel foam composite electrode was 0.38 mg).
Example 10:
RuO2The preparation of the foamed nickel composite electrode (ruthenium oxide content is 0.38 mg) comprises the following steps:
1) accurately weighing 30mg of ruthenium chloride, adding the ruthenium chloride into 1ml of n-butyl alcohol, and then carrying out ultrasonic treatment for 10 minutes to fully dissolve the ruthenium chloride and the n-butyl alcohol to obtain a ruthenium chloride-n-butyl alcohol solution for later use; soaking the foamed nickel in dilute hydrochloric acid with the concentration of 0.5% for 10min, taking out the foamed nickel, washing the foamed nickel with residual hydrochloric acid on the surface of the foamed nickel by using water, and drying to obtain clean foamed nickel for later use;
2) using a pipette to drop 20 μ L of the ruthenium chloride-n-butanol solution obtained in step 1) on the cleaned 1x1 pingThe method comprises the following steps of (1) calcining the nickel foam with square centimeters at high temperature in a muffle furnace in an air environment, wherein the process comprises the following steps: under the air environment, uniformly heating from room temperature to 450 ℃ at the speed of 7 ℃/min, keeping the constant temperature for 30min, and naturally cooling to room temperature to obtain RuO2Foamed nickel composite electrode (RuO)2The ruthenium oxide content in the nickel foam composite electrode was 0.38 mg).
Example 11:
RuO2The preparation of the foamed nickel composite electrode (ruthenium oxide content is 0.38 mg) comprises the following steps:
1) accurately weighing 30mg of ruthenium chloride, adding the ruthenium chloride into 1ml of water, and then carrying out ultrasonic treatment for 10 minutes to fully dissolve the ruthenium chloride to obtain a ruthenium chloride-water solution for later use; soaking the foamed nickel in dilute hydrochloric acid with the concentration of 0.5% for 10min, taking out the foamed nickel, washing the residual hydrochloric acid on the surface of the foamed nickel by using water, and drying to obtain the cleaned foamed nickel for later use;
2) taking 20 mu L of the ruthenium chloride-water solution obtained in the step 1) by using a pipette, dripping the ruthenium chloride-water solution on clean 1x1 square centimeter of foamed nickel, and then calcining the solution at high temperature in a muffle furnace in an air environment, wherein the process comprises the following steps: under the air environment, uniformly heating from room temperature to 450 ℃ at the speed of 7 ℃/min, keeping the constant temperature for 30min, and naturally cooling to room temperature to obtain RuO2Foamed nickel composite electrode (RuO)2The ruthenium oxide content in the nickel foam composite electrode was 0.38 mg).
Example 12:
RuO2The preparation of the foamed nickel composite electrode (ruthenium oxide content is 0.38 mg) comprises the following steps:
1) accurately weighing 30mg of ruthenium chloride, adding the ruthenium chloride into 1ml of ethanol, and then carrying out ultrasonic treatment for 10 minutes to fully dissolve the ruthenium chloride to obtain a ruthenium chloride-water solution for later use; soaking the foamed nickel in dilute hydrochloric acid with the concentration of 0.5% for 10min, taking out the foamed nickel, washing the residual hydrochloric acid on the surface of the foamed nickel by using water, and drying to obtain the cleaned foamed nickel for later use;
2) taking 20 mu L of the ruthenium chloride-ethanol solution obtained in the step 1) by using a liquid transfer gun, dripping the solution on clean 1x1 square centimeter of foamed nickel, and then calcining the solution at high temperature in a muffle furnace in an air environmentThe process is as follows: under the air environment, uniformly heating from room temperature to 450 ℃ at the speed of 7 ℃/min, keeping the constant temperature for 30min, and naturally cooling to room temperature to obtain RuO2Foamed nickel composite electrode (RuO)2The ruthenium oxide content in the nickel foam composite electrode was 0.38 mg).
Example 13:
weighing 0.5g of ruthenium chloride, and calcining the ruthenium chloride in a muffle furnace at high temperature in an air environment, wherein the process comprises the following steps: under the air environment, the temperature is uniformly raised to 450 ℃ from the room temperature at the speed of 7 ℃/min, the constant temperature is kept for 30min, and then the RuO is obtained after natural cooling to the room temperature2Grinding, and weighing 3.8mg RuO2Adding 100 mu L of Dupont nafion solution (mass fraction of 5%) and 450 mu L of absolute ethyl alcohol, and performing ultrasonic treatment for 30min to uniformly disperse the solution to obtain the product containing RuO2The mixed solution of (1). Then, 55. mu.L of RuO-containing solution was aspirated2Coating the mixture of (1 x1 cm)2Drying the Ni foam in an infrared drying lamp to obtain RuO2A foamed nickel composite electrode.
Application example 1: the performance of the composite electrodes prepared in examples 1 to 13 was tested:
the composite electrodes prepared in examples 1 to 13 are applied to the test process of electrolytic deuterium evolution reaction when being used as working electrodes respectively: mixing RuO2The foamed nickel composite electrode is used as a working electrode, the platinum sheet is used as a counter electrode, and the saturated Ag/AgCl electrode is used as a reference electrode. The experimental conditions are that the test is carried out in 0.1mol/L NaOD heavy water solution at normal temperature and normal pressure, and the standard voltage range is 0V-0.6V.
According to the test procedure described above, sampling analysis was carried out at different time points during the continuous electrolysis. FIGS. 3 and 4 are graphs showing the variation of the amount of deuterium generated during the electrolysis process with the electrolysis time when the composite electrodes prepared in examples 1 to 11 were used as working electrodes, respectively. As can be seen from fig. 3 and 4: conditions in the process of synthesizing the composite electrode (examples 1 to 3) were changed to find RuO2The content has a great influence on the effect of producing deuterium in RuO2The content of 0.38mg can achieve an optimal effect. By varying the conditions during the synthesis of the composite electrode (examples 1, 4 and 5), it was found that the calcination temperature had a strong effect on the production of deuteriumThe great influence can reach an optimal effect when the calcining temperature is 450 ℃. Conditions (examples 1, 6 to 8) in the process of synthesizing the composite electrode are changed to find that the calcination time has great influence on the deuterium production effect, and when the calcination time is 30 minutes, an optimal effect can be achieved. Changing the conditions during the synthesis of the composite electrode (examples 1, 9 and 10) revealed that the rate of temperature rise during high temperature calcination of the catalyst had a great effect on the deuterium production, and that an optimum effect was achieved while maintaining the rate of temperature rise of 5 ℃/min. By varying the solvents in which ruthenium chloride is dissolved (examples 2, 11 and 12), it was found that the deuterium-producing effect of the resulting catalyst is significantly better than that of the catalyst prepared using water or ethanol as the solvent, when n-butanol is used as the solvent.
RuO prepared in embodiments 1, 11 to 13 of the present invention2The comparative graph of the performance test results of the nickel foam composite electrode in the application of preparing deuterium by electrolyzing deuterium from deuterium is shown in FIG. 5, and RuO formed by directly calcining ruthenium chloride in air atmosphere can be seen from FIG. 52The catalytic activity of the catalyst is relatively poor.
Wherein, when the composite electrode prepared in example 1 is used as a working electrode to carry out electrolysis reaction, the change relationship of the current density in the electrolysis process along with time is shown in figure 6, and it can be seen from figure 6 that the stability of the current density in the electrolysis process is good, and the service life of the composite electrode is good.
After the continuous electrolytic reaction for 1800s, the composite electrode of example 2 was washed clean with water and dried, and its SEM image is shown in fig. 2. The results of fig. 1-2 show that the composite electrode of example 2 has no significant structural change before and after the reaction, and maintains good structural stability.
In conclusion, conditions such as ruthenium oxide content, high-temperature calcination heating rate and the like of the composite electrode are changed, so that the deuterium gas produced by the heavy water electrolysis is greatly influenced, an optimal experimental condition can be obtained by regulation, the cost is saved, the reaction efficiency is improved, the existing technology for producing deuterium gas by an alkali metal deuterium oxide method is replaced, and the industrial technology for producing deuterium gas by the heavy water electrolysis is realized.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.

Claims (7)

1. RuO2A foamed nickel composite electrode, characterized in that the composite electrode is made of RuO2As active ingredient, RuO2RuO loaded on foamed nickel carrier per square centimeter of foamed nickel2The content is 0.38 mg;
the RuO2The preparation method of the foamed nickel composite electrode comprises the following steps:
1) adding a ruthenium precursor into n-butanol, and uniformly dispersing by ultrasonic to obtain a ruthenium precursor-n-butanol solution for later use; soaking the foamed nickel in dilute hydrochloric acid with the concentration of 0.5wt.% for 10min, taking out the foamed nickel, washing the residual hydrochloric acid on the surface of the foamed nickel by using water, and drying to obtain the cleaned foamed nickel for later use;
2) dripping the ruthenium precursor-n-butyl alcohol solution obtained in the step 1) on the cleaned foam nickel, and then calcining at high temperature in a muffle furnace in an air environment; naturally cooling to room temperature after calcination is finished, thus obtaining the RuO2A foamed nickel composite electrode;
in the step 2), the high-temperature calcination process in the muffle furnace comprises the following steps: under the air environment, the temperature is uniformly raised to 450 ℃ from the room temperature at the speed of 5 ℃/min, then the temperature is kept for 30min, and then the temperature is naturally cooled to the room temperature.
2. A RuO as set forth in claim 12The nickel foam composite electrode is characterized in that in the step 1), the ruthenium precursor is ruthenium chloride, the ratio of the mass of the ruthenium precursor to the volume of n-butanol is 20-40:1, the unit of the mass is mg, and the unit of the volume is mL.
3. A RuO as set forth in claim 22The nickel foam composite electrode is characterized in that in the step 1), the ruthenium precursor is ruthenium chloride, the ratio of the mass of the ruthenium precursor to the volume of n-butanol is 30:1, the unit of the mass is mg, and the unit of the volume is mL.
4. A RuO as set forth in claim 22The foam nickel composite electrode is characterized in that when the ruthenium precursor-n-butyl alcohol solution in the step 2) is dripped on the foam nickel, the volume of the ruthenium precursor-n-butyl alcohol solution dripped on each square centimeter of the foam nickel is 10 muL-30 muL.
5. A RuO as set forth in claim 42The foamed nickel composite electrode is characterized in that when the ruthenium precursor-n-butyl alcohol solution in the step 2) is dripped on the foamed nickel, the volume of the ruthenium precursor-n-butyl alcohol solution dripped on each square centimeter of the foamed nickel is 20 mu L.
6. The RuO of claim 12The foamed nickel composite electrode is applied to the preparation of deuterium gas by electrolyzing heavy water.
7. The RuO of claim 62The application of the foamed nickel composite electrode in the preparation of deuterium gas by electrolyzing heavy water is characterized in that the electrolysis process is carried out in a single-tank electrolytic cell, a three-electrode electrolysis system is adopted, and the RuO is adopted2The foamed nickel composite electrode is used as a working electrode, a platinum wire is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and the reaction of preparing deuterium gas by electrolyzing heavy water is carried out.
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