CN112962115A - Foamed nickel loaded sulfide electrocatalyst and preparation method and application thereof - Google Patents
Foamed nickel loaded sulfide electrocatalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a sulfide electrocatalyst loaded by foamed nickel and a preparation method and application thereof. Compared with the prior art, the electrocatalyst has the advantages of low cost, high efficiency, sulfuration resistance and dual functions of sulfur ion oxidation and water decomposition hydrogen analysis.
Description
Technical Field
The invention relates to the technical field of electrocatalytic material preparation, electrochemical sulfur ion oxidation and hydrogen evolution, in particular to a nickel foam loaded sulfide electrocatalyst and a preparation method and application thereof.
Background
Hydrogen energy is an energy substance with high calorific value, cleanliness, renewability and the like. With the ever decreasing reserves of oil and the climate change due to greenhouse gas emissions, there is an increasing demand for clean energy. In recent years, the vigorous spread of fuel cell vehicles has brought hydrogen energy to a new stateTherefore, the hydrogen production process has very important practical significance for the requirements of the current society. The electrochemical decomposition of water to produce hydrogen is considered to be one of the most potential technologies for producing clean hydrogen energy. However, the anodic reaction-oxygen evolution reaction (4 OH) involved in electrochemically decomposing water-→2H2O+O2+4e-) Has higher oxidation-reduction potential (O)2/H21.23V vs. she), a lot of energy is consumed.
On the other hand, hydrogen sulfide gas is a toxic waste gas from the oil refining and natural gas extraction industries, and the amount of hydrogen sulfide discharged per year can reach the million ton level. The removal and resource utilization of hydrogen sulfide gas are very important at present, and the industrial waste gas hydrogen sulfide can be absorbed by alkali liquor to become dissolved sulfur ions and then oxidized into elemental sulfur by an electrochemical method. The electrochemical oxidation half-reaction of sulfide ions can be represented as S2-→S+2e-. The redox potential of this reaction is only 0.17V vs. she, which is much lower than that of the oxygen evolution reaction. Therefore, the sulfur ion oxidation reaction is used for replacing the oxygen precipitation reaction, so that the electric energy required by the electrolyzed water is greatly saved, and simultaneously, the high-added-value hydrogen and the elemental sulfur are produced, the high energy consumption of the traditional electrolyzed water hydrogen production and the removal and recovery of hydrogen sulfide pollutants are realized, and the two purposes are achieved.
The invention patent CN 110607531A of Dazongzhe and Kokoku relates to electrochemical treatment H2S gas, but the anode involves an intermediate medium (e.g. hydroquinone, K)3Fe(CN)6、EDTA-Fe2+) Mediated by a two-step indirect reaction, and the catalytic electrode material is monofunctional (only capable of oxidizing H)2S), while hydrogen production at the cathode end requires different catalytic electrodes, thus limiting its production scale and increasing technical complexity. On the other hand, the traditional metal electrode material such as copper is directly used for sulfur ion electrocatalytic oxidation, and the activity and the stability are reduced due to the corrosion effect of sulfur ions on the electrode. The graphene-coated metal (Co/Ni alloy) nanoparticle electrode disclosed in the Dalian junction can realize high-efficiency sulfur ion oxidation reaction and certain corrosion resistance (Zhang et al, Energy)&Environmental Science,2020,13(1):119-The preparation method comprises the steps of refluxing and precipitating cobalt nickel hydroxide to the surface of a silicon dioxide nanosphere at 100 ℃, sintering at 600 ℃ in hydrogen argon reducing gas to form a nano alloy, depositing a graphite layer on the surface of the nano alloy by using a chemical vapor deposition method, etching the silicon dioxide nanosphere by using acid to form a metal nanoparticle catalytic material coated by the graphite layer, obtaining a metal and sulfur ion isolation layer, and protecting the metal material. This causes the defects of complicated material preparation process, high energy consumption caused by high-temperature sintering and the like, and limits the large-scale production of the material.
Disclosure of Invention
The invention aims to provide a sulfide electrocatalyst loaded on foamed nickel and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme: a preparation method of a sulfide electrocatalyst loaded on foamed nickel takes foamed nickel as a substrate, firstly, metal simple substances, metal oxides or metal hydroxide nanoparticles are grown on the surface of the foamed nickel in situ by a hydrothermal method, and then the foamed nickel with the metal simple substances, the metal oxides or the metal hydroxide nanoparticles grown on the surface is immersed in a sulfur-containing solution for room temperature vulcanization to obtain the sulfide electrocatalyst loaded on the foamed nickel. The foam nickel has a three-dimensional network macroporous structure, can have high specific surface area and conductivity, and has rich material sources and low price. According to the invention, the foamed nickel is used as a substrate, the metal sulfide grows in situ, extra coating of an electrode material and use of a binder are not required, the preparation process is simple and controllable, and the catalyst growing on the surface of the substrate has a stable structure. The vertically grown metal sulfide nano structure is attached to the surface of the foamed nickel, so that the low charge transfer resistance is realized, the mass transfer distance is shortened, and the electrochemical activity is improved.
Further, the preparation method specifically comprises the following steps:
(1) sequentially immersing foamed nickel into a hydrochloric acid solution, deionized water and absolute ethyl alcohol, ultrasonically cleaning to remove impurities, and then drying;
(2) adding a certain amount of metal nitrate solution or mixed solution of metal nitrate and urea into a hydrothermal reaction kettle, keeping the liquid filling rate at 30-70%, soaking the foamed nickel obtained in the step (1) into the solution, sealing the reaction kettle, heating to 80-200 ℃, reacting for 2-12 h, cooling the reaction kettle to room temperature, taking out the foamed nickel, washing and drying at room temperature to obtain a catalyst precursor material loaded with the foamed nickel;
(3) soaking the foamed nickel loaded with the catalyst precursor material into a sulfur-containing solution, keeping the temperature at 10-35 ℃ for 2 min-12 h, taking out, washing with deionized water, and finally drying at room temperature to obtain the foamed nickel loaded sulfide electrocatalyst.
Furthermore, the thickness of the foamed nickel in the step (1) is 0.05-0.50 cm, and the foamed nickel is cut into 2 multiplied by 3cm2The size of the block is 0.1-6.0 mol.L-1The ultrasonic cleaning time is 10 min-1 h. The foamed nickel is cut into a size and a shape which can stand in the kettle body and can be completely immersed by the liquid level.
The metal nitrate in the step (2) is one or more of copper nitrate, nickel nitrate, cobalt nitrate or ferric nitrate; the concentration of the metal nitrate solution is 0.02-0.5 mol.L-1In the mixed solution of the metal nitrate and the urea, the concentration of the urea is not more than 100 g.L-1。Cu2+、Ni2+、Co2+And Fe3+All are 3d transition metal element cations, have the characteristics of low price and easy obtainment and can be applied in large scale. The function of urea is to provide an alkaline environment, allowing the metal to combine with hydroxide ions to form a metal hydroxide or oxide. The concentration of the specific metal nitrate is added to ensure that enough metal oxide or hydroxide is uniformly loaded on the surface of the foamed nickel, and the pH can be regulated and controlled by proper amount of urea, so that the forming process of the metal oxide or hydroxide can be regulated and controlled.
The sulfur-containing solution in the step (3) is a sodium sulfide solution or a mixed solution of sulfur and sodium sulfide, and the concentration of the sodium sulfide solution is 1-2 mol.L-1The concentration of sulfur in the mixed solution of sulfur and sodium sulfide is not more than 2 mol.L-1. Hydrothermal synthesis due to the generally lower solubility product of sulfides compared to oxides or hydroxidesOxide (e.g. Cu)2O) or hydroxides (Ni (OH)2Etc.), sodium sulfide is added, wherein the sulfur ion can replace oxygen or hydroxide with metal sulfide. On the other hand, when the valence state of the metal ions changes in the hydrothermal process, for example, copper and nickel are replaced to generate elemental copper, the weakly-oxidizing elemental sulfur can oxidize the elemental copper into cuprous sulfide. The reaction rate can be adjusted by adding a proper amount of sulfur ions and sulfur simple substances, and an optimal result is obtained.
A sulfide electrocatalyst loaded by foamed nickel is prepared by adopting the preparation method.
The application of the nickel foam supported sulfide electrocatalyst is to use the nickel foam supported sulfide electrocatalyst for electrolyzing aqueous solution of sulfide.
Furthermore, the cathode and anode catalytic electrodes for electrolyzing the sulfide aqueous solution are both the foamed nickel-supported sulfide electrocatalyst, the anolyte is a mixed aqueous solution of sulfide and hydroxide, the electrolysis product is sulfur, the catholyte is an aqueous solution of hydroxide, and the electrolysis product is hydrogen.
Furthermore, the sulfide is one or more of sodium sulfide, potassium sulfide and hydrogen sulfide, and the hydroxide is one or two of sodium hydroxide and potassium hydroxide. In the industry, alkaline solution is generally used for absorbing hydrogen sulfide gas to form alkaline to neutral solution (due to the limitation of pKa, sulfur ion in acid is unstable), and the used alkali is usually sodium hydroxide or potassium hydroxide, wherein potassium hydroxide has the advantages of small ionic solvation radius of potassium ion, fast ionic mobility and benefit for electrochemical reaction, and sodium hydroxide is cheaper and has lower cost in large-scale application.
The anolyte and the catholyte are alkaline. The oxidation reaction is facilitated in the alkaline environment, and the defect that the non-noble metal is unstable in the acidic environment is avoided.
The invention discloses a preparation method of a nickel foam loaded metal sulfide electrocatalyst and application thereof in alkaline electrolysis hydrogen precipitation and sulfur ion oxidation reaction, wherein a metal simple substance, a metal oxide or gold is firstly constructed on the surface of nickel foamBelongs to hydroxide nanosheets and then is vulcanized at room temperature to form the hierarchical porous metal sulfide/foamed nickel, has high activity and stability, remarkably improves the performance of electrocatalytic hydrogen evolution and sulfur ion oxidation reaction, realizes the same catalytic electrode for a cathode and an anode, has the characteristics of simple structure, high electrolytic efficiency, stable electrode and the like, can drive sulfur ion oxidation to produce sulfur and water to decompose to produce hydrogen under the condition of a two-electrode system by only 0.69V voltage, and has the reaction current density as high as 100 mA-cm-2。
Compared with the prior art, the invention has the following advantages:
1. the invention has the double functions of directly oxidizing sulfur ions to produce sulfur (without indirect oxidation-reduction reaction) and reducing hydrogen ions to produce hydrogen, has stable electrodes, high activity, simple process and low energy consumption, particularly has mild material synthesis temperature which is not more than 200 ℃, has less synthesis steps, only needs a hydrothermal and room temperature vulcanization two-step method, obtains a catalyst with good effect and stability, can drive sulfur ions to oxidize to produce sulfur and decompose water to produce hydrogen under the condition of a two-electrode system by only 0.69V voltage, and has the reaction current density as high as 100 mA-cm-2；
2. The invention selects the foam nickel as the substrate, has a three-dimensional network macroporous structure, can provide high specific surface area and conductivity, and has rich material sources and low price;
3. according to the invention, the foamed nickel is used as a substrate, the metal sulfide grows in situ, extra coating of an electrode material and use of a binder are not required, the preparation process is simple and controllable, and the catalyst growing on the surface of the substrate has a stable structure;
4. the growth of the metal sulfide is regulated and controlled by trying to regulate and control different metal cations, hydrothermal temperature and vulcanization time, so that the catalytic activity and stability are regulated and controlled;
5. the vertically grown metal sulfide nano structure is attached to the surface of the foamed nickel, so that the low charge transfer resistance is realized, the mass transfer distance is shortened, and the electrochemical activity is improved;
6. the invention adopts the foamed nickel as the substrate to construct the metal sulfide nanometer bifunctional electrolytic hydrogen precipitation and sulfur ion oxidation catalyst, has high activity and stability, has low requirement on equipment, and can be used for electrochemically decomposing hydrogen sulfide pollutants on a large scale;
7. the nickel foam loaded sulfide electrocatalyst has the characteristics of high efficiency, low cost and vulcanization resistance, has the double functions of sulfur ion oxidation and water decomposition hydrogen analysis, and solves the problems of sulfur ion corrosion, low electrochemical stability and activity and the like in the prior art, thereby realizing large-scale electrochemical sulfur ion oxidation and water decomposition hydrogen production and H2The treatment of S waste gas and the production of high value-added substances are a new scheme combining environmental management and clean hydrogen energy production, and have important significance and application prospect.
Drawings
FIG. 1 is an X-ray diffraction pattern of a cuprous sulfide/nickel foam electrode of example 1;
FIG. 2 is a scanning electron microscope photograph of the cuprous sulfide/nickel foam electrode of example 1;
FIG. 3 is a polarization curve of the cuprous sulfide/nickel foam electrode catalyzed sulfur ion oxidation reaction of example 7;
FIG. 4 is a comparison of polarization curve tests for the two-electrode system of the example 9 cuprous sulfide/nickel foam electrode catalyzed alkaline hydrogen sulfide decomposition versus conventional water decomposition;
FIG. 5 is a graph showing the stability of the decomposition of basic hydrogen sulfide catalyzed by the cuprous sulfide/nickel foam electrode of example 9.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation processes are given, but the scope of the invention is not limited to the following examples.
The electrochemical performance test and application experiment of the catalytic electrode described in the following examples include:
1. electrochemical sulfur ion oxidation half reaction experiment: selecting a three-electrode system to measure the oxidation reaction activity of the sulfur ions, taking the prepared metal sulfide/foamed nickel electrode as a working electrode (anode), and using NaOH + Na with certain concentration2Taking the S aqueous solution as an anolyte and Ag/AgCl as a reference electrode, and electrifying the Pt sheetThe electrode is used as a counter electrode (cathode), and the catholyte is 1 mol.L-1NaOH aqueous solution, and a cathode and an anode are separated by a Nafion ion exchange membrane.
2. Electrochemical water decomposition hydrogen half-reaction experiment: a three-electrode system is selected to test the hydrogen evolution reaction activity, and the cathode and the anolyte are 1 mol.L-1NaOH aqueous solution, a cathode (hydrogen evolution electrode) electrode material is a metal sulfide/foam nickel electrode, an anode electrode material is a Pt sheet electrode, Ag/AgCl is used as a reference electrode, and a cathode and an anode are separated by a Nafion ion exchange membrane.
3. An electrochemical experiment of a sulfur ion oxidation and water decomposition hydrogen production two-electrode system is as follows: using NaOH aqueous solution with a certain concentration as cathode electrolyte, and using NaOH + Na with a certain concentration2The aqueous solution of S is used as an anolyte, and the cathode and the anode are separated by a Nafion ion exchange membrane. The cathode electrode material and the anode electrode material are both the metal sulfide/foamed nickel catalytic electrode material.
Example 1
A method for preparing a nickel foam supported sulfide electrocatalyst, comprising the steps of:
a) firstly, soaking foamed nickel (with the thickness of 1mm) in HCl solution, deionized water and absolute ethyl alcohol in sequence, ultrasonically cleaning to remove impurities, and then drying.
b) In the second step, 14mL of 0.028 mol. L is taken-1Copper nitrate and 21 g.L-1And (3) putting the mixed solution of urea into a hydrothermal reaction kettle, and keeping the filling rate at 70%. And putting the cleaned foamed nickel into the solution, sealing the reaction kettle, heating to 120 ℃ for hydrothermal reaction for 6 hours, taking out the cuprous oxide/foamed nickel electrode material when the kettle is cooled to room temperature, washing and drying at room temperature.
c) Thirdly, the obtained electrode material is soaked in a sulfur-containing solution by 1 mol.L-1Na2And S is kept for 12 hours, and the electrode is washed by deionized water after being taken out and dried at room temperature to obtain the cuprous sulfide/foamed nickel electrode.
The X-ray diffraction pattern of the obtained cuprous sulfide/foamed nickel electrode is shown in figure 1, three characteristic peaks of cuprous sulfide can be seen, and the successful synthesis of cuprous sulfide materials is proved.
The scanning electron microscope image is shown in fig. 2, and it can be seen that cuprous sulfide is in a sheet structure, and the three-dimensional structure can effectively increase the specific surface area of the electrode material, thereby improving the catalytic activity of the electrode.
Example 2
A preparation method of a cuprous sulfide/foamed nickel catalyst comprises the following steps:
a) the first step is the same as in example 1.
b) In the second step, 14mL of 0.02 mol/L-1 copper nitrate solution was placed in a hydrothermal reaction vessel with a fill rate of 70%. And putting the cleaned foamed nickel into the solution, sealing the reaction kettle tightly, heating to 150 ℃ for hydrothermal reaction for 5 hours, taking out the copper/foamed nickel after the kettle is cooled to room temperature, washing and drying at room temperature.
c) Thirdly, the obtained electrode material is soaked into a sulfur-containing solution (2 mol. L)-1Na2S+2mol·L-1S) keeping for 12 hours, taking out, washing with deionized water and drying at room temperature to obtain the cuprous sulfide/foamed nickel electrode.
Example 3
A preparation method of a nickel sulfide/foamed nickel catalyst comprises the following steps:
a) the first step is the same as in example 1.
b) In the second step, 14mL of 0.028 mol.L is taken-1Nickel nitrate and 21 g.L-1And (3) putting the mixed solution of urea into a hydrothermal reaction kettle, and keeping the filling rate at 70%. And putting the cleaned nickel foam into the solution, sealing the reaction kettle tightly, heating to 120 ℃ for hydrothermal reaction for 6 hours, taking out the nickel foam when the kettle is cooled to room temperature, washing and drying at room temperature.
c) Thirdly, the obtained electrode material is soaked in a sulfur-containing solution by 1 mol.L-1Na2And (4) keeping the S for 12h, taking out, washing with deionized water, and drying at room temperature to obtain the nickel sulfide/foamed nickel electrode.
Example 4
A preparation method of a cobalt sulfide/foamed nickel catalyst comprises the following steps:
a) the first step is the same as in example 1.
b) In the second step, 14mL of 0.028 mol.L is taken-1Cobalt nitrate and 21 g.L-1And (3) putting the mixed solution of urea into a hydrothermal reaction kettle, and keeping the filling rate at 70%. And putting the cleaned nickel foam into the solution, sealing the reaction kettle tightly, heating to 120 ℃ for hydrothermal reaction for 6 hours, taking out the nickel foam when the kettle is cooled to room temperature, washing and drying at room temperature.
c) Thirdly, the obtained electrode material is soaked in a sulfur-containing solution by 1 mol.L-1Na2And (4) keeping the S for 12h, taking out, washing with deionized water, and drying at room temperature to obtain the cobalt sulfide/foamed nickel electrode.
Example 5
A preparation method of an iron sulfide/foamed nickel catalyst comprises the following steps:
a) the first step is the same as the first step in the first embodiment.
b) In the second step, 14mL of 0.028 mol.L is taken-1Ferric nitrate with 21 g.L-1And (3) putting the mixed solution of urea into a hydrothermal reaction kettle, and keeping the filling rate at 70%. And putting the cleaned nickel foam into the solution, sealing the reaction kettle tightly, heating to 120 ℃ for hydrothermal reaction for 6 hours, taking out the nickel foam when the kettle is cooled to room temperature, washing and drying at room temperature.
c) Thirdly, the obtained electrode material is soaked in a sulfur-containing solution by 1 mol.L-1Na2And (4) keeping the S for 12h, taking out, washing with deionized water, and drying at room temperature to obtain the iron sulfide/foamed nickel electrode.
Example 6
The cuprous sulfide/foamed nickel electrode obtained in example 1 was subjected to a three-electrode electrochemical performance test to examine the activity and stability of electrochemical sulfur oxide ions.
The cuprous sulfide/nickel foam electrode synthesized in example 1 was used as the working electrode (anode) and 1 mol. L-1NaOH+1mol·L-1Na2Aqueous S solution as anolyte (simulated H)2Solution of S absorbed in NaOH aqueous solution, the same applies below) at 1 mol. L-1NaOH aqueous solution is used as catholyte (hydrogen evolution reaction), a Pt sheet electrode is used as a counter electrode (cathode), the cathode and the anode in a three-electrode system are separated by a Nafion membrane, and Ag/AgCl is used as a reference electrode。
The catalyst obtained in example 1 was used in a three-electrode electrolytic sulfur oxide ion experiment to test polarization curves. RHE was obtained at a potential of 0.48V vs. 100 mA/cm-2And passes a constant current test (100mA cm)-2) The current density obtained by the material is kept for 12 hours without obvious attenuation. After the reaction, colorless gas is obtained at the cathode and is identified as H by GC-TCD (Agilent 7890A)2(ii) a The anode product was investigated by three-electrode electrolysis at 100 mA-cm-2Acidifying the anode liquid after current density electrolysis for 25h with concentrated sulfuric acid, filtering to obtain yellow solid product, and analyzing the product by X-ray diffraction to obtain elemental sulfur (S)8). The XRD result, the ultraviolet-visible spectrum test and the solution color change can be used for presuming that the reaction process is that sulfur ions are oxidized to lose electrons and then are combined with other sulfur ions to form a chain to obtain a polysulfide intermediate, and further the electrons form crown type S8A molecule. This shows that the catalyst synthesized in example 1 has good catalytic activity and can successfully oxidize and recover sulfur ions into elemental sulfur.
Example 7
The cuprous sulfide/foamed nickel electrode obtained in example 2 was subjected to a three-electrode electrochemical performance test to investigate the activity and stability of electrochemical sulfur oxide ions.
The cuprous sulfide/nickel foam electrode synthesized in example 2 was used as the working electrode (anode) and 1 mol. L-1NaOH+1mol·L-1Na2The S aqueous solution is used as an anode electrolyte, the NaOH aqueous solution is used as a cathode (hydrogen evolution reaction) electrolyte, the Pt sheet electrode is used as a counter electrode (cathode), the cathode and the anode in a three-electrode system are separated by a Nafion film, and Ag/AgCl is used as a reference electrode. The polarization curve was tested by inserting a reference electrode and a working electrode into an anode cell as shown in FIG. 3 to test the performance of the sulfide ion oxidation reaction on the cuprous sulfide/nickel foam surface by applying a voltage of 5 mV. s-1The linear scan test of (2) can obtain an initial potential of about 0.24V and 10 and 100 mA-cm at potentials of 0.25 and 0.34V vs. RHE, respectively-2The current density of (a) shows that the catalyst of example 2 has a higher sulfur ion oxidation activity and a better effect than the catalyst obtained in example 1.
Example 8
And (4) observing the hydrogen evolution reaction of the metal sulfide/foamed nickel electrode. The electrode obtained in example 1 was used as a working electrode (cathode, hydrogen dissociation reaction for water), and 1 mol. L-1NaOH aqueous solution is used as the cathode electrolyte; the cathode and the anode in the three-electrode system are separated by a Nafion membrane; the anodic oxygen evolution reaction is carried out at a concentration of 1 mol.L-1NaOH is used as electrolyte, and a Pt electrode is used as a counter electrode (anode); the three electrodes use Ag/AgCl as a reference electrode. When the current density reaches 10mA cm-2The cathode overpotential was 180mV, and bubble formation was observed at the cathode, and the gas was collected by the drainage method and analyzed by GC-TCD to be hydrogen. After the system is electrolyzed for a long time of 12 hours, the current is not obviously attenuated, and only is increased by 40 mV. This indicates that the cuprous sulfide/nickel foam material exhibits good catalytic activity and stability for the hydrogen evolution reaction.
Example 9
The cuprous sulfide/foamed nickel electrode prepared in example 1 is used to construct a two-electrode system to decompose sodium sulfide aqueous solution to produce hydrogen (cathode) and elemental sulfur (anode). Shown in FIG. 4, at 1 mol. L-1NaOH aqueous solution as catholyte, at 1 mol. L-1NaOH+1mol·L-1Na2The aqueous solution of S is used as an anolyte, the cathode and the anode in a two-electrode system are separated by a Nafion membrane, and after the solution and the system resistance (iR correction, 27 omega) are removed, the polarization curve of the two electrodes is measured, and the current density reaches 10 mA-cm-2The required voltage is only 0.48V (solid line) with respect to the reversible hydrogen electrode. According to the LSV curve data in FIG. 4, the concentration of the catalyst is 10mA cm under the catalysis system of cuprous sulfide/foamed nickel-2Electrolysis, calculated to give a hydrogen yield of 36.6mol/kWh, reduced the energy consumption by 78% compared to the 10.3mol/kWh hydrogen yield calculated by direct electrochemical decomposition of water (dashed line), and at the same time treated hydrogen sulfide gas. Further, as shown in FIG. 5, after 6 days of long-term constant current electrolysis test (in which the catholyte and anolyte were updated every other two days), the two-electrode system was maintained at a current density of 10mA cm-2The material has good stability and can carry out long-time electrolytic reaction.
Example 10
A method for preparing a nickel foam supported sulfide electrocatalyst, comprising the steps of:
a) firstly, soaking foamed nickel (with the thickness of 0.5mm) in HCl solution, deionized water and absolute ethyl alcohol in sequence, ultrasonically cleaning to remove impurities, and then drying.
b) In the second step, 10mL of 0.25 mol.L is taken-1The copper nitrate solution is put into a hydrothermal reaction kettle, and the filling rate is kept at 50%. And (3) putting the cleaned foamed nickel into the solution, sealing the reaction kettle, heating to 80 ℃ for hydrothermal reaction for 2 hours, taking out the cuprous oxide/foamed nickel electrode material when the kettle is cooled to room temperature, washing and drying at room temperature.
c) Thirdly, the obtained electrode material is soaked in a sulfur-containing solution by 1.5 mol.L-1Na2And S is kept for 2min, and the electrode is taken out, washed by deionized water and dried at room temperature to obtain the cuprous sulfide/foamed nickel electrode.
Example 11
A method for preparing a nickel foam supported sulfide electrocatalyst, comprising the steps of:
a) firstly, soaking foamed nickel (with the thickness of 5mm) in HCl solution, deionized water and absolute ethyl alcohol in sequence, ultrasonically cleaning to remove impurities, and then drying.
b) Second, take 6mL of 0.5 mol. L-1Copper nitrate and 100 g.L-1The mixed solution of urea is put into a hydrothermal reaction kettle, and the filling rate is kept at 30%. And (3) putting the cleaned foamed nickel into the solution, sealing the reaction kettle, heating to 200 ℃ for hydrothermal reaction for 12 hours, taking out the cuprous oxide/foamed nickel electrode material when the kettle is cooled to room temperature, washing and drying at room temperature.
c) Thirdly, the obtained electrode material is soaked into a sulfur-containing solution (2 mol. L)-1Na2S+1mol·L-1S) keeping for 5h, taking out, washing with deionized water and drying at room temperature to obtain the cuprous sulfide/foamed nickel electrode.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention. All the equivalent structures or equivalent processes performed by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A preparation method of a sulfide electrocatalyst loaded on foamed nickel is characterized in that the foamed nickel is used as a substrate, firstly, metal simple substances, metal oxides or metal hydroxide nanoparticles are grown on the surface of the foamed nickel in situ by a hydrothermal method, and then the foamed nickel with the metal simple substances, the metal oxides or the metal hydroxide nanoparticles grown on the surface is immersed in a sulfur-containing solution for room-temperature vulcanization to obtain the sulfide electrocatalyst loaded on foamed nickel.
2. The method of claim 1, comprising the steps of:
(1) sequentially immersing foamed nickel into a hydrochloric acid solution, deionized water and absolute ethyl alcohol, ultrasonically cleaning to remove impurities, and then drying;
(2) adding a metal nitrate solution or a mixed solution of metal nitrate and urea into a hydrothermal reaction kettle, keeping the liquid filling rate at 30-70%, soaking the foamed nickel obtained in the step (1) into the solution, sealing the reaction kettle, heating to 80-200 ℃, reacting for 2-12 h, cooling the reaction kettle to room temperature, taking out the foamed nickel, washing and drying at room temperature to obtain a catalyst precursor material loaded with the foamed nickel;
(3) soaking the foamed nickel loaded with the catalyst precursor material into a sulfur-containing solution, keeping the temperature at 10-35 ℃ for 2 min-12 h, taking out, washing with deionized water, and finally drying at room temperature to obtain the foamed nickel loaded sulfide electrocatalyst.
3. The method of claim 2, wherein the nickel foam of step (1) has a thickness of 0.05 to 0.50cm and a hydrochloric acid solution concentration of 0.1 to 6.0 mol-L-1The ultrasonic cleaning time is 10 min-1 h.
4. The method for preparing the nickel foam supported sulfide electrocatalyst according to claim 2, wherein the metal nitrate in step (2) is one or more of copper nitrate, nickel nitrate, cobalt nitrate or iron nitrate; the concentration of the metal nitrate solution is 0.02-0.5 mol.L-1In the mixed solution of the metal nitrate and the urea, the concentration of the urea is not more than 100 g.L-1。
5. The method for preparing the nickel foam supported sulfide electrocatalyst according to claim 2, wherein the sulfur-containing solution in step (3) is a sodium sulfide solution or a mixed solution of sulfur and sodium sulfide, and the concentration of the sodium sulfide solution is 1-2 mol-L-1The concentration of sulfur in the mixed solution of sulfur and sodium sulfide is not more than 2 mol.L-1。
6. A foamed nickel-supported sulfide electrocatalyst characterized by being prepared by the preparation method of any one of claims 1 to 5.
7. Use of a nickel foam supported sulphide electrocatalyst according to claim 6, characterised in that the nickel foam supported sulphide electrocatalyst is used for the electrolysis of aqueous sulphide solutions.
8. The use of the foamed nickel-supported sulfide electrocatalyst according to claim 7, wherein the cathode and anode catalytic electrodes for electrolysis of aqueous sulfide solution are both the foamed nickel-supported sulfide electrocatalyst, the anolyte is a mixed aqueous solution of sulfide and hydroxide, the electrolysis product is sulfur, the catholyte is an aqueous hydroxide solution, and the electrolysis product is hydrogen.
9. The use of the nickel foam supported sulfide electrocatalyst according to claim 8, wherein the sulfide is one or more of sodium sulfide, potassium sulfide and hydrogen sulfide, and the hydroxide is one or two of sodium hydroxide and potassium hydroxide.
10. Use of a foamed nickel supported sulfide electrocatalyst according to claim 8, wherein the anolyte and catholyte are alkaline.
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| CN113445072A (en) * | 2021-06-29 | 2021-09-28 | 湖北大学 | Foamed nickel composite electrode and preparation method and application thereof |
| CN114737213A (en) * | 2022-03-30 | 2022-07-12 | 江苏大学 | FeS @ SW/NF electrocatalyst and preparation method and application thereof |
| CN114807956A (en) * | 2022-04-11 | 2022-07-29 | 西南石油大学 | Preparation method of in-situ growth nano array catalyst applied to hydrogen sulfide hydrogen production |
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| CN115026121A (en) * | 2022-06-13 | 2022-09-09 | 中南大学 | Method and device for electrokinetic remediation of heavy metal contaminated soil by using nanostructure foam iron-based sulfide three-dimensional electrode |
| CN115341166A (en) * | 2022-10-19 | 2022-11-15 | 有研工程技术研究院有限公司 | Preparation method of nickel-based vulcanized material |
| CN114807956B (en) * | 2022-04-11 | 2024-05-17 | 西南石油大学 | Preparation method of in-situ growth nano-array catalyst applied to hydrogen sulfide hydrogen production |
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