CN116219490A - Preparation and application of high-performance low-noble metal electrode for electrolyzed water - Google Patents
Preparation and application of high-performance low-noble metal electrode for electrolyzed water Download PDFInfo
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Abstract
The invention discloses a preparation and application of a high-performance low-noble metal electrode for electrolyzed water, which relates to the technical field of electrocatalytic materials and comprises the following steps: s1: placing the foamy copper into ultrapure water and hydrochloric acid for cleaning and ultrasonic treatment for 30min, and then cleaning with water, ethanol or acetone; s2: mixing copper salt with a stabilizer, and magnetically stirring for 20-60min to form precursor copper salt solution; s3: dissolving precursor nickel salt, precursor M salt and alkaline precipitant in ultrapure water to prepare a precursor a; s4: calcining the precursor a in air at 200-600 ℃ to obtain a precursor CuO-Cu@NixMyOz; ruthenium chloride solution is used as electrolyte, and constant voltage is set at CuO-Cu@Ni x MyO z Ru is electrodeposited on the surface, and the low noble metal electrode with the core-shell structure CuO-Cu@NixMyOz@Ru catalyst for electrolyzed water is prepared. The prepared core-shell structure catalyst is beneficial to improving the stability and activity of the catalyst.
Description
Technical Field
The invention relates to the technical field of electrocatalytic materials, in particular to preparation and application of a high-performance low-noble metal electrode for water electrolysis.
Background
With the current shortage of fossil fuels and the increasing problem of environmental pollution, scientists are motivated to put energy into the energy field, and a sustainable pollution-free clean energy is sought. Hydrogen energy has attracted considerable attention as an efficient, clean, renewable energy carrier. In many hydrogen production processes, water electrolysis hydrogen production stands out from the advantages of environmental protection and independence of fossil fuel. The water electrolysis process involves two semi-reactive Hydrogen Evolution Reactions (HER) and Oxygen Evolution Reactions (OER). However, both HER and OER are less efficient, requiring four electron transfer during OER than HER, involving more intermediates, which requires a higher kinetic barrier, which is a major bottleneck for OER. Currently, electrolyzed water OER catalysts include two classes: noble metal catalysts and non-noble metal catalysts. The noble metal catalyst mainly comprises iridium dioxide (IrO) 2 ) Ruthenium dioxide (RuO) 2 ) And the like have higher catalytic activity and lower overpotential, but are unfavorable for large-scale industrialized application due to high cost and low reserves of noble metals. Although the non-noble metal catalyst reduces the cost, the catalytic activity and the stability of the non-noble metal catalyst are far lower than those of the noble metal catalyst.
Based on the problems, the invention provides a method for doping a small amount of noble metal, high specific surface area, high specific activity, low cost and simple preparation method, which takes foam copper as a substrate and loads a bimetallic ferronickel oxide doped ruthenium oxygen evolution reaction catalyst on the surface of the substrate by utilizing a hydrothermal method, a high-temperature roasting method and an electrodeposition method.
Disclosure of Invention
The invention aims to provide a preparation method and application of a high-performance low-noble metal electrode for water electrolysis, so as to solve the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions: the preparation method of the high-performance low-noble metal electrode for the electrolyzed water comprises the following steps:
s1: placing the foamy copper into ultrapure water and hydrochloric acid for cleaning and ultrasonic treatment for 30min, then cleaning with water, ethanol or acetone, and vacuum drying for 2-12h at 50-80 ℃;
s2: mixing copper salt and a stabilizer, magnetically stirring for 20-60min to form a precursor copper salt solution, electrodepositing a layer of metal Cu on the surface of a foam copper substrate layer under the condition of constant voltage at normal temperature, cleaning, drying, then placing the treated foam copper into a muffle furnace, reacting for 2-5 h at 150-400 ℃, and then cooling to the room temperature to obtain CuO-Cu; the preferred temperature is 200-300℃and the reaction time is 2-3 hours.
S3: dissolving precursor nickel salt, precursor M salt and alkaline precipitant in ultrapure water, stirring, then placing the stirred solution into treated foamy copper for hydrothermal reaction, and separating and drying to obtain a precursor a;
s4: calcining the precursor a in air at 200-600 ℃ to obtain a precursor CuO-Cu@Ni after calcining x M y O z ;
S5: the ruthenium chloride solution is used as electrolyte, and under the normal temperature condition, the precursor CuO-Cu@Ni x M y O z Under constant voltage condition for the carrier, cuO-Cu@Ni x M y O z Ru is electrodeposited on the surface to prepare CuO-Cu@Ni with a core-shell structure x M y O z An electrode of low noble metal for electrolysis of water of a Ru catalyst.
Preferably, the stabilizer in the S2 is polyvinylpyrrolidone (PVP), tritonX-100 (C) 14 H 22 O(C 2 H 4 O) n ) One or both of which has a concentration of 0.01M to 0.18M, preferably a concentration of 0.05M to 0.15M.
Preferably, the precursor nickel salt in the S3 is Ni (NO 3 ) 2 ·6H 2 O、NiCl 2 ·6H 2 O、NiSO 4 ·6H 2 O, wherein the concentration of nickel ions is 0.1 mM-1.0M, preferably 0.05M-0.5M, and the precursor ferric salt is Fe (NO) 3 ) 3 ·9H 2 O、FeCl 3 ·6H 2 O、Fe 2 (SO 4 ) 3 ·H 2 O, wherein the concentration of iron ions is 0.2 mM-2.0M, preferably 0.08M-0.3M.
Preferably, the alkaline precipitant in the step S3 is one or more than two of urea, ammonia water, sodium bicarbonate, sodium carbonate and ammonium bicarbonate, the concentration of the alkaline precipitant is 1 mmol/L-1.0 mol/L, the molar concentration ratio of the alkaline precipitant to nickel in the precursor nickel salt solution is 0.5:1-50:1, and the molar concentration ratio of the alkaline precipitant to iron in the precursor iron salt solution is 1:2-50:1.
Preferably, the temperature of the hydrothermal reaction in the step S3 is 110-200 ℃ and the time is 4-14 h.
Preferably, the precursor a in the step S4 is placed in a muffle furnace for calcination, and the process conditions of calcination are as follows: the temperature rising rate is controlled at 2 ℃/min, and the temperature is raised to 200 ℃ to 600 ℃ for calcination for 2 hours.
Preferably, the concentration of the ruthenium chloride solution in the S5 is 1 mmol/L-1.0 mol/L, the constant voltage is 0.07V (vs. SHE), the deposition time is 300-800S, and then the deposition is 300-800S at 0.05V vs. SHE.
Preferably, M is one or more than two of transition metals Fe, co, W, mo, wherein Ru content is 2wt% to 40wt%, ni content is 15wt% to 20wt%, fe content is 30wt% to 45wt%, and O content is 15wt% to 33wt%.
The invention also discloses a high-performance low-noble metal electrode for the electrolyzed water, which is prepared by the preparation method of the high-performance low-noble metal electrode for the electrolyzed water.
The invention also discloses application of the high-performance low-noble metal electrode for the electrolyzed water, which is applied to the electrocatalytic alkaline oxygen evolution reaction.
The invention has the technical effects and advantages that:
1. the high-performance low-noble metal electrode for electrolyzed water provided according to the above embodiment is: the preparation method of the bimetallic ferronickel oxide doped ruthenium oxygen evolution reaction catalyst comprises the steps of selecting copper foam as a carrier, selecting ferronickel as a metal source, preparing a precursor through an electrodeposition method, a hydrothermal method and a high Wen Tui fire method, and preparing the core-shell structure bimetallic ferronickel oxide doped ruthenium oxygen evolution reaction catalyst through the precursor by adopting the electrodeposition method.
2. According to the bimetallic nickel-iron oxide doped ruthenium oxygen evolution reaction catalyst, firstly, foam copper is selected as a carrier, the carrier is electrodeposited and roasted in air, cuO nano particles are formed on the surface of the foam copper, so that the conductivity of the whole system and the stability of a catalyst material can be enhanced, and a large number of electrons are transported and more active sites are exposed; in addition, nickel iron is selected as a metal source, so that the catalytic activity of the whole system can be better improved; in addition, the doping of noble metal ruthenium can better improve the stability and catalytic activity of the catalyst. Because the preparation process adopts the synthesis of hydrothermal and high-temperature annealing-electrodeposition methods, the whole synthesis process is simple, the raw materials are low in price and wide in source, and the large-scale production can be performed.
3. Tests show that the bimetallic nickel-iron oxide doped ruthenium oxygen evolution reaction catalyst has good catalytic activity (the current density is 50mA cm) -2 The overpotential is 377 mV), which shows that the electrocatalytic oxygen evolution reaction activity of the bimetallic nickel-iron oxide doped ruthenium catalyst is better performed in alkaline environment. Compared with the prior art, the invention has the advantages of wide raw material sources, low raw material price and simple and clear preparation process, is beneficial to improving the hydrogen production efficiency of water electrolysis and is beneficial to promoting the wide use of hydrogen energy.
4. According to the bimetallic ferronickel oxide doped ruthenium oxygen evolution reaction catalyst, the duration and the temperature parameters of the hydrothermal reaction in the preparation process enable the prepared precursor to be stable in structure and good in crystallinity; the calcination temperature in the high-temperature annealing process is timely long in parameter, so that the precursor is fully oxidized, and the doping of noble metal ruthenium ensures that the final product has stable structure, high catalytic activity and good conductivity. Therefore, the invention shows excellent performance and good stability in the performance test process.
Drawings
FIG. 1 is a linear sweep voltammogram of the bimetallic nickel iron oxide doped ruthenium oxygen evolution reaction catalyst obtained in example 1 in 1M KOH solution;
FIG. 2 is a graph showing the linear voltammogram of the bimetallic nickel iron oxide doped ruthenium oxygen evolution reaction catalyst obtained in example 1 in 1M KOH solution at different reaction temperatures for the same reaction duration in a hydrothermal reaction;
FIG. 3 is a graph showing the linear voltammogram of the bimetallic nickel iron oxide doped ruthenium oxygen evolution reaction catalyst obtained in example 1 in 1M KOH solution at the same reaction temperature and for different reaction durations in a hydrothermal reaction;
FIG. 4 is a graph showing the linear voltammogram of the bimetallic nickel iron oxide doped ruthenium oxygen evolution reaction catalyst obtained in example 1 in 1M KOH solution at different high annealing temperatures;
FIG. 5 is a plot of time-voltage in 1M KOH solution for the bimetallic nickel iron oxide doped ruthenium oxygen evolution reaction catalyst obtained in example 1;
FIG. 6 is an SEM image of a bimetallic nickel iron oxide doped ruthenium oxygen evolution reaction catalyst obtained in example 1.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The invention provides a preparation method of a high-performance low-noble metal electrode for electrolyzed water, which is shown in fig. 1-6, and comprises the following steps:
s1: placing the foamy copper into ultrapure water and hydrochloric acid for cleaning and ultrasonic treatment for 30min, then cleaning with water, ethanol or acetone, and vacuum drying for 2-12h at 50-80 ℃;
s2: mixing copper salt and a stabilizer, magnetically stirring for 20-60min to form a precursor copper salt solution, electrodepositing a layer of metal Cu on the surface of a foam copper substrate layer under the condition of constant voltage at normal temperature, cleaning, drying, then placing the treated foam copper into a muffle furnace, reacting for 2-5 h at 150-400 ℃, and then cooling to the room temperature to obtain CuO-Cu; the preferred temperature is 200-300℃and the reaction time is 2-3 hours.
S3: dissolving precursor nickel salt, precursor M salt and alkaline precipitant in ultrapure water, stirring, then placing the stirred solution into treated foamy copper for hydrothermal reaction, and separating and drying to obtain a precursor a;
s4: calcining the precursor a in air at 200-600 ℃ to obtain a precursor CuO-Cu@Ni after calcining x M y O z ;
S5: the ruthenium chloride solution is used as electrolyte, and under the normal temperature condition, the precursor CuO-Cu@Ni x M y O z Under constant voltage condition for the carrier, cuO-Cu@Ni x M y O z Ru is electrodeposited on the surface to prepare CuO-Cu@Ni with a core-shell structure x M y O z An electrode of low noble metal for electrolysis of water of a Ru catalyst.
The stabilizer in S2 is polyvinylpyrrolidone (PVP) or TritonX-100 (C) 14 H 22 O(C 2 H 4 O) n ) One or both of which has a concentration of 0.01M to 0.18M, preferably a concentration of 0.05M to 0.15M.
The precursor nickel salt in S3 is Ni (NO) 3 ) 2 ·6H 2 O、NiCl 2 ·6H 2 O、NiSO 4 ·6H 2 O, wherein the concentration of nickel ions is 0.1 mM-1.0M, preferably 0.05M-0.5M, and the precursor ferric salt is Fe (NO) 3 ) 3 ·9H 2 O、FeCl 3 ·6H 2 O、Fe 2 (SO 4 ) 3 ·H 2 O, wherein the concentration of iron ions is 0.2 mM-2.0M, preferably 0.08M-0.3M.
And S3, the alkaline precipitant is one or more than two of urea, ammonia water, sodium bicarbonate, sodium carbonate and ammonium bicarbonate, wherein the concentration of the alkaline precipitant is 1 mmol/L-1.0 mol/L, the molar concentration ratio of the alkaline precipitant to nickel in the precursor nickel salt solution is 0.5:1-50:1, and the molar concentration ratio of the alkaline precipitant to iron in the precursor iron salt solution is 1:2-50:1.
S3, the temperature of the hydrothermal reaction is 110-200 ℃ and the time is 4-14 h.
And S4, placing the precursor a in a muffle furnace for calcination, wherein the process conditions of the calcination are as follows: the temperature rising rate is controlled at 2 ℃/min, and the temperature is raised to 200 ℃ to 600 ℃ for calcination for 2 hours.
The concentration of the ruthenium chloride solution in the S5 is 1 mmol/L-1.0 mol/L, the constant voltage is 0.07V (vs. SHE), the deposition time is 300-800S, and then the deposition is 300-800S at 0.05V vs. SHE.
M is one or more than two of transition metals Fe, co, W, mo, wherein Ru content is 2-40 wt%, ni content is 15-20 wt%, fe content is 30-45 wt%, and O content is 15-33 wt%.
The invention also discloses a high-performance low-noble metal electrode for the electrolyzed water, which is prepared by the preparation method of the high-performance low-noble metal electrode for the electrolyzed water.
The invention also discloses application of the high-performance low-noble metal electrode for the electrolyzed water, which is applied to the electrocatalytic alkaline oxygen evolution reaction.
1. Cutting a certain amount of foamy copper, tabletting, placing into ultrapure water and hydrochloric acid, cleaning with ultrasonic for 30min, cleaning with water, ethanol or acetone, and vacuum drying at 60deg.C for 6 hr;
2. 55mL of 0.2M CuCl 2 ·2H 2 Mixing the O solution and 165mL of 0.06M PVP solution as electrolyte, electrodepositing for 1800s under the condition of constant voltage of-0.3V (vs. Ag/AgCl) to obtain a layer of metal Cu, cleaning, drying, putting the treated foam copper into a muffle furnace, reacting at 300 ℃ for 2h, and cooling to room temperature to obtain CuO-Cu;
3. selecting Ni (NO) 3 ) 2 ·6H 2 O is used as a precursor nickel salt solution, fe (NO 3 ) 3 ·9H 2 O is used as a precursor ferric salt solution, wherein the concentration of nickel ions is 0.05M; the concentration of iron ions is 0.1M, a certain amount of urea is added as an alkaline precipitant, so that the molar concentration ratio of the alkaline precipitant to nickel ions is 20:1, and the magnetic stirring is carried out for 30min;
4. transferring the mixed solution and the treated foam copper into a hydrothermal reaction kettle, heating in a high-temperature oven at 180 ℃ for 12 hours, cooling to room temperature, taking out the cooled foam nickel, flushing with water and absolute ethyl alcohol, and vacuum drying at 60 ℃ for 12 hours to obtain a dried precursor a;
5. calcining the precursor a in air at high temperature, controlling the heating rate to be 2 ℃/min, heating to 300 ℃ and roasting for 2 hours, and obtaining the precursor CuO-Cu@NiFe 2 O 4 ;
6. 100mL of 10mmol/L ruthenium chloride solution is taken as electrolyte, the deposition time is 300-800s under the constant voltage of 0.07V (vs. SHE), then 300-800s is deposited under the constant voltage of 0.05V vs. SHE, and the core-shell structure CuO-Cu@NiFe is obtained after washing 2 O 4 An @ Ru catalyst.
FIG. 1 corresponds to a linear sweep voltammogram of a bimetallic nickel iron oxide doped ruthenium oxygen evolution reaction catalyst in 1M KOH solution.
As can be seen from fig. 1, the overpotential of the bimetallic nickel iron oxide doped ruthenium oxygen evolution reaction catalyst is significantly lower than that of the undoped noble metal ruthenium catalyst: bimetallic nickel-iron oxide doped ruthenium oxygen evolution reaction catalyst with current density of 50mA cm -2 The time overpotential is 377mV, and compared with the time overpotential when the nickel-iron oxide reaches the same current density, the time overpotential is respectively reduced by 66mV, thereby proving that the bimetallic nickel-iron oxide doped ruthenium oxygen evolution reaction catalyst has higher catalytic activity on the electrolytic water oxygen evolution reaction.
Example 2
As compared with example 1, the same operations as in example 1 except that the hydrothermal reaction temperature was changed to 110℃130℃ 150℃and 200℃respectively, the performance was weaker than that of the material having a reaction temperature of 180℃as shown in FIG. 2.
Example 3
In comparison with example 1, the same operations as in example 1 were carried out except that the solvothermal reaction time periods were changed to 4h, 6h, 8h and 14h, respectively, and the properties were weaker than those of the material having a time period of 12h as shown in FIG. 3.
Example 4
As compared with example 1, the same operations as in example 1 were carried out except that the high-temperature annealing temperature was changed to 200℃at 400℃at 500℃at 600℃in this order, and the properties were weaker than those of the material having an annealing temperature of 300℃as shown in FIG. 4.
Comparative example 1
1. Cutting a certain amount of foamy copper, tabletting, placing into ultrapure water and hydrochloric acid, cleaning with ultrasonic for 30min, cleaning with water, ethanol or acetone, and vacuum drying at 60deg.C for 6 hr;
2. selecting Ni (NO) 3 ) 2 ·6H 2 O is used as a precursor nickel salt solution, fe (NO 3 ) 3 ·9H 2 O is used as a precursor ferric salt solution, wherein the concentration of nickel ions is 0.05M; the concentration of iron ions is 0.1M, a certain amount of urea is added as an alkaline precipitant, so that the molar concentration ratio of the alkaline precipitant to nickel ions is 20:1, and the magnetic stirring is carried out for 30min;
3. transferring the mixed solution and the treated foam copper into a hydrothermal reaction kettle, heating in a high-temperature oven at 180 ℃ for 12 hours, cooling to room temperature, taking out the cooled foam nickel, flushing with water and absolute ethyl alcohol, and vacuum drying at 60 ℃ for 12 hours to obtain a dried precursor a;
4. calcining the precursor a in air at high temperature, controlling the heating rate to be 2 ℃/min, heating to 300 ℃ and roasting for 2 hours, and obtaining the precursor Cu@NiFe 2 O 4 ;
5. 100mL of 10mmol/L ruthenium chloride solution is taken as electrolyte, the deposition time is 300-800s under the constant voltage of 0.07V (vs. SHE), then 300-800s is deposited under the constant voltage of 0.05V vs. SHE, and the core-shell structure Cu@NiFe is obtained after washing 2 O 4 An @ Ru catalyst.
Comparative example 2
1. Cutting a certain amount of foamy copper, tabletting, placing into ultrapure water and hydrochloric acid, cleaning with ultrasonic for 30min, cleaning with water, ethanol or acetone, and vacuum drying at 60deg.C for 6 hr;
2. 55mL of 0.2M CuCl 2 ·2H 2 Mixing O solution and 165mL 0.06M PVP solution as electrolyte, electrodepositing for 1800s under the condition of constant voltage of-0.3V (vs. Ag/AgCl) to obtain a layer of metal Cu, cleaning, drying, putting the treated foam copper into a muffle furnace, and reacting at 300 DEG C2h, then cooling to room temperature to obtain CuO-Cu; the method comprises the steps of carrying out a first treatment on the surface of the
3. Selecting Ni (NO) 3 ) 2 ·6H 2 O is used as a precursor nickel salt solution, fe (NO 3 ) 3 ·9H 2 O is used as a precursor ferric salt solution, wherein the concentration of nickel ions is 0.05M; the concentration of iron ions is 0.1M, a certain amount of urea is added as an alkaline precipitant, so that the molar concentration ratio of the alkaline precipitant to nickel ions is 20:1, and the magnetic stirring is carried out for 30min;
4. transferring the mixed solution and the treated foam copper into a hydrothermal reaction kettle, heating in a high-temperature oven at 180 ℃ for 12 hours, cooling to room temperature, taking out the cooled foam nickel, flushing with water and absolute ethyl alcohol, and vacuum drying at 60 ℃ for 12 hours to obtain a dried precursor a;
5. 100mL of 10mmol/L ruthenium chloride solution is used as electrolyte, the deposition time is 300-800s under the constant voltage of 0.07V (vs. SHE), then the deposition time is 300-800s under the constant voltage of 0.05V vs. SHE, and the CuO-Cu@NiFe LDH@Ru catalyst with a core-shell structure is obtained after washing.
Comparative example 3
1. Cutting a certain amount of foamy copper, tabletting, placing into ultrapure water and hydrochloric acid, cleaning with ultrasonic for 30min, cleaning with water, ethanol or acetone, and vacuum drying at 60deg.C for 6 hr;
2. 55mL of 0.2M CuCl 2 ·2H 2 Mixing the O solution and 165mL of 0.06M PVP solution as electrolyte, electrodepositing for 1800s under the condition of constant voltage of-0.3V (vs. Ag/AgCl) to obtain a layer of metal Cu, cleaning, drying, putting the treated foam copper into a muffle furnace, reacting at 300 ℃ for 2h, and cooling to room temperature to obtain CuO-Cu;
3. co (NO) 3 ) 3 ·6H 2 O is used as a precursor nickel salt solution, fe (NO 3 ) 3 ·9H 2 O is used as a precursor ferric salt solution, wherein the concentration of cobalt ions is 0.05M; the concentration of iron ions is 0.1M, a certain amount of urea is added as an alkaline precipitant, so that the molar concentration ratio of the alkaline precipitant to cobalt ions is 20:1, and the magnetic stirring is carried out for 30min;
4. transferring the mixed solution and the treated foam copper into a hydrothermal reaction kettle, heating in a high-temperature oven at 180 ℃ for 12 hours, cooling to room temperature, taking out the cooled foam nickel, flushing with water and absolute ethyl alcohol, and vacuum drying at 60 ℃ for 12 hours to obtain a dried precursor a;
5. calcining the precursor a in air at high temperature, controlling the heating rate to be 2 ℃/min, heating to 300 ℃ and roasting for 2 hours, and obtaining the precursor CuO-Cu@CoFe x O y ;
6. 100mL of 10mmol/L ruthenium chloride solution is taken as electrolyte, the deposition time is 300-800s under the constant voltage of 0.07V (vs. SHE), then 300-800s is deposited under the constant voltage of 0.05V vs. SHE, and the core-shell structure CuO-Cu@CoFe is obtained after washing x O y An @ Ru catalyst.
Comparative example 4
1. Cutting a certain amount of foamy copper, tabletting, placing into ultrapure water and hydrochloric acid, cleaning with ultrasonic for 30min, cleaning with water, ethanol or acetone, and vacuum drying at 60deg.C for 6 hr;
2. 55mL of 0.2M CuCl 2 ·2H 2 Mixing the O solution and 165mL of 0.06M PVP solution as electrolyte, electrodepositing for 1800s under the condition of constant voltage of-0.3V (vs. Ag/AgCl) to obtain a layer of metal Cu, cleaning, drying, putting the treated foam copper into a muffle furnace, reacting at 300 ℃ for 2h, and cooling to room temperature to obtain CuO-Cu;
3. 100mL of 10mmol/L ruthenium chloride solution is used as electrolyte, the deposition time is 300-800s under the constant voltage of 0.07V (vs. SHE), then the deposition time is 300-800s under the constant voltage of 0.05V vs. SHE, and the core-shell structure CuO-Cu@Ru catalyst is obtained after washing.
Comparative example 5
1. Cutting a certain amount of foamy copper, tabletting, placing into ultrapure water and hydrochloric acid, cleaning with ultrasonic for 30min, cleaning with water, ethanol or acetone, and vacuum drying at 60deg.C for 6 hr;
2. 55mL of 0.2M CuCl 2 ·2H 2 Mixing O solution and 165mL 0.06M PVP solution as electrolyte, electrodepositing for 1800s under the condition of constant voltage of-0.3V (vs. Ag/AgCl) to obtain a layer of metal Cu, cleaning and dryingThen placing the treated foamy copper into a muffle furnace, reacting for 2 hours at 300 ℃, and then cooling to room temperature to obtain CuO-Cu;
3. selecting Ni (NO) 3 ) 2 ·6H 2 O is used as a precursor nickel salt solution, fe (NO 3 ) 3 ·9H 2 O is used as a precursor ferric salt solution, wherein the concentration of nickel ions is 0.05M; the concentration of iron ions is 0.1M, a certain amount of urea is added as an alkaline precipitant, so that the molar concentration ratio of the alkaline precipitant to nickel ions is 20:1, and the magnetic stirring is carried out for 30min;
4. transferring the mixed solution and the treated foam copper into a hydrothermal reaction kettle, heating in a high-temperature oven at 180 ℃ for 12 hours, cooling to room temperature, taking out the cooled foam nickel, flushing with water and absolute ethyl alcohol, and vacuum drying at 60 ℃ for 12 hours to obtain a dried precursor a;
5. calcining the precursor a in air at high temperature, controlling the heating rate to be 2 ℃/min, heating to 300 ℃ and roasting for 2 hours, and obtaining the precursor CuO-Cu@NiFe 2 O 4 。
FIG. 2 corresponds to a linear sweep voltammogram of a bimetallic nickel iron oxide doped ruthenium oxygen evolution reaction catalyst in 1M KOH solution at different hydrothermal reaction temperatures.
As can be seen from fig. 2, the overpotential of the bimetallic nickel-iron oxide doped ruthenium oxygen evolution reaction catalyst at 180 ℃ is significantly lower than that of the other reaction temperatures; the oxygen evolution reaction catalyst of the bimetallic nickel-iron oxide doped ruthenium reaches 50mA cm -2 The overpotential is 377mV when the current density is higher than that of the compound obtained at other reaction temperatures, thereby proving that the bimetallic nickel-iron oxide doped ruthenium oxygen evolution reaction catalyst has optimal catalytic activity on the electrolytic water oxygen evolution reaction at the reaction temperature of 180 ℃.
FIG. 3 corresponds to a linear sweep voltammogram of a bimetallic nickel iron oxide doped ruthenium oxygen evolution reaction catalyst in 1M KOH solution at different hydrothermal reaction times.
As can be seen from FIG. 3, the overpotential of the bimetallic nickel-iron oxide doped ruthenium oxygen evolution reaction catalyst at the reaction time of 12h is obviously lower than that of other reaction timesIs a catalyst of (a); the bimetallic nickel-iron oxide doped ruthenium oxygen evolution reaction catalyst reaches 50mA cm -2 The overpotential is 377mV when the current density is the same as that of the complex obtained in other reaction time, thereby proving that the bimetallic nickel-iron oxide doped ruthenium oxygen evolution reaction catalyst has optimal catalytic activity on electrolytic water oxygen evolution in the reaction time of 12 h.
FIG. 4 corresponds to a linear sweep voltammogram of a bimetallic nickel iron oxide doped ruthenium oxygen evolution reaction catalyst in 1M KOH solution at different high temperature annealing temperatures.
As can be seen from fig. 4, the overpotential of the bimetallic nickel-iron oxide doped ruthenium oxygen evolution reaction catalyst at the high temperature annealing temperature of 300 ℃ is significantly lower than that of the catalyst at other annealing temperatures; the bimetallic nickel-iron oxide doped ruthenium oxygen evolution reaction catalyst reaches 50mA cm -2 The overpotential is 377mV when the current density is higher than that of the catalyst obtained by other annealing temperatures, thereby proving that the bimetallic nickel-iron oxide doped ruthenium oxygen evolution reaction catalyst has optimal catalytic activity on electrolytic water oxygen evolution when the annealing temperature is 300 ℃.
FIG. 5 is a graph showing the time-voltage curve of the bimetallic nickel iron oxide doped ruthenium oxygen evolution reaction catalyst obtained in example 1 in 1M KOH solution.
From fig. 5, it can be seen that the reaction time of the bimetallic nickel-iron oxide doped ruthenium oxygen evolution reaction catalyst in 1M KOH solution reaches 25h voltage without attenuation, which indicates that the bimetallic nickel-iron oxide doped ruthenium oxygen evolution reaction catalyst has electrocatalytic oxygen evolution reaction activity and electrochemical stability under alkaline environment.
SEM images of the obtained bimetallic nickel iron oxide doped ruthenium oxygen evolution reaction catalyst were taken using a scanning electron microscope (model Quanta 400FEG, manufacturer FEI company, usa) and shown in fig. 6. It can be seen from fig. 6 that the obtained bimetallic nickel-iron oxide doped ruthenium oxygen evolution reaction catalyst has a sheet structure.
The invention has the following functions and effects:
according to the preparation method of the bimetallic nickel-iron oxide doped ruthenium oxygen evolution reaction catalyst provided by the embodiment, foam copper is selected as a carrier, nickel iron is selected as a metal source, a precursor is prepared through an electrodeposition method, a hydrothermal method and a high Wen Tui fire method, and then the core-shell structure bimetallic nickel-iron oxide doped ruthenium oxygen evolution reaction catalyst is prepared through the electrodeposition method of the precursor.
According to the bimetallic nickel-iron oxide doped ruthenium oxygen evolution reaction catalyst, firstly, foam copper is selected as a carrier, the carrier is electrodeposited and roasted in air, cuO nano particles are formed on the surface of the foam copper, so that the conductivity of the whole system and the stability of a catalyst material can be enhanced, and a large number of electrons are transported and more active sites are exposed; in addition, nickel iron is selected as a metal source, so that the catalytic activity of the whole system can be better improved; in addition, the doping of noble metal ruthenium can better improve the stability and catalytic activity of the catalyst. Because the preparation process adopts the synthesis of hydrothermal and high-temperature annealing-electrodeposition methods, the whole synthesis process is simple, the raw materials are low in price and wide in source, and the large-scale production can be performed.
Tests show that the bimetallic nickel-iron oxide doped ruthenium oxygen evolution reaction catalyst has good catalytic activity (the current density is 50mA cm) -2 The overpotential is 377 mV), which shows that the electrocatalytic oxygen evolution reaction activity of the bimetallic nickel-iron oxide doped ruthenium catalyst is better performed in alkaline environment. Compared with the prior art, the invention has the advantages of wide raw material sources, low raw material price and simple and clear preparation process, is beneficial to improving the hydrogen production efficiency of water electrolysis and is beneficial to promoting the wide use of hydrogen energy.
According to the bimetallic ferronickel oxide doped ruthenium oxygen evolution reaction catalyst, the duration and the temperature parameters of the hydrothermal reaction in the preparation process enable the prepared precursor to be stable in structure and good in crystallinity; the calcination temperature in the high-temperature annealing process is timely long in parameter, so that the precursor is fully oxidized, and the doping of noble metal ruthenium ensures that the final product has stable structure, high catalytic activity and good conductivity. Therefore, the invention shows excellent performance and good stability in the performance test process.
Claims (10)
1. A preparation method of a high-performance low-noble metal electrode for electrolyzed water is characterized by comprising the following steps: the method comprises the following steps:
s1: placing the foamy copper into ultrapure water and hydrochloric acid for cleaning and ultrasonic treatment for 30min, then cleaning with water, ethanol or acetone, and vacuum drying for 2-12h at 50-80 ℃;
s2: mixing copper salt and a stabilizer, magnetically stirring for 20-60min to form a precursor copper salt solution, electrodepositing a layer of metal Cu on the surface of a foam copper substrate layer under the condition of constant voltage at normal temperature, cleaning, drying, then placing the treated foam copper into a muffle furnace, reacting for 2-5 h at 150-400 ℃, and then cooling to the room temperature to obtain CuO-Cu.
S3: dissolving precursor nickel salt, precursor M salt and alkaline precipitant in ultrapure water, stirring, then placing the stirred solution into treated foamy copper for hydrothermal reaction, and separating and drying to obtain a precursor a;
s4: calcining the precursor a in air at 200-600 ℃ to obtain a precursor CuO-Cu@Ni after calcining x M y O z ;
S5: the ruthenium chloride solution is used as electrolyte, and under the normal temperature condition, the precursor CuO-Cu@Ni x M y O z Under constant voltage condition for the carrier, cuO-Cu@Ni x M y O z Ru is electrodeposited on the surface to prepare CuO-Cu@Ni with a core-shell structure x M y O z An electrode of low noble metal for electrolysis of water of a Ru catalyst.
2. The method for preparing the high-performance low-noble metal electrode for electrolyzed water according to claim 1, wherein the method comprises the following steps: the stabilizer in S2 is polyvinylpyrrolidone (PVP) or TritonX-100 (C) 14 H 22 O(C 2 H 4 O) n ) One or two of the above, the concentration of which is 0.01M-0.18M.
3. The method for preparing the high-performance low-noble metal electrode for electrolyzed water according to claim 2, wherein the method comprises the following steps: the precursor nickel salt in the S3 is Ni (NO) 3 ) 2 ·6H 2 O、NiCl 2 ·6H 2 O、NiSO 4 ·6H 2 O, wherein the concentration of nickel ions is 0.1 mM-1.0M, preferably 0.05M-0.5M, and the precursor ferric salt is Fe (NO) 3 ) 3 ·9H 2 O、FeCl 3 ·6H 2 O、Fe 2 (SO 4 ) 3 ·H 2 O, wherein the concentration of iron ions is 0.2 mM-2.0M.
4. A method for preparing a high-performance low-noble metal electrode for electrolyzed water according to claim 3, characterized in that: the alkaline precipitant in the step S3 is one or more than two of urea, ammonia water, sodium bicarbonate, sodium carbonate and ammonium bicarbonate, the concentration of the alkaline precipitant is 1 mmol/L-1.0 mol/L, the molar concentration ratio of the alkaline precipitant to nickel in the precursor nickel salt solution is 0.5:1-50:1, and the molar concentration ratio of the alkaline precipitant to iron in the precursor iron salt solution is 1:2-50:1.
5. The method for preparing the high-performance low-noble metal electrode for electrolyzed water according to claim 4, wherein the method comprises the following steps: the temperature of the hydrothermal reaction in the step S3 is 110-200 ℃ and the time is 4-14 h.
6. The method for preparing the high-performance low-noble metal electrode for electrolyzed water according to claim 5, wherein the method comprises the following steps: and (4) placing the precursor a in the step S4 into a muffle furnace for calcination, wherein the process conditions of calcination are as follows: the temperature rising rate is controlled at 2 ℃/min, and the temperature is raised to 200 ℃ to 600 ℃ for calcination for 2 hours.
7. The method for preparing the high-performance low-noble metal electrode for electrolyzed water according to claim 6, wherein the method comprises the following steps: the concentration of the ruthenium chloride solution in the S5 is 1 mmol/L-1.0 mol/L, the constant voltage is 0.07V or 0.05V (vs. SHE), and the deposition time is 300-800S.
8. The method for preparing the high-performance low-noble metal electrode for electrolyzed water according to claim 7, wherein the method comprises the following steps: m is one or more than two of transition metals Fe, co, W, mo, wherein Ru content is 2-40 wt%, ni content is 15-20 wt%, fe content is 30-45 wt%, and O content is 15-33 wt%.
9. A high-performance low-noble metal electrode for electrolytic water, characterized by being prepared by the method for preparing a high-performance low-noble metal electrode for electrolytic water according to any one of claims 1 to 8.
10. The use of a high performance low noble metal electrode for electrolysis of water according to claim 9, wherein: the high-performance low-noble metal electrode for electrolyzed water is applied to an electrocatalytic alkaline oxygen evolution reaction.
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CN117187870B (en) * | 2023-09-21 | 2024-05-28 | 北京未来氢能科技有限公司 | Preparation method of low iridium catalyst for hydrogen production by water electrolysis |
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