CN113957456A - Nickel-based alkaline electrolytic water catalyst with co-doped combination heterostructure and preparation method thereof - Google Patents
Nickel-based alkaline electrolytic water catalyst with co-doped combination heterostructure and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of electrochemical catalytic materials, and discloses a nickel-based alkaline electrolyzed water catalyst with a co-doped combination heterostructure and a preparation method thereof, wherein the molecular formula of the catalyst is as follows: EO-Cu3‑Fe2‑Ni50and/NF. The catalyst of the invention is an alkaline electrolytic water catalyst loaded on foamed nickel, and is prepared by Cu,Co-doping of Fe in combination with Ni (OH)2Construction of/Ni heterostructure, modulation of oxidation state of active metal center Ni and provision of abundant Ni (OH)2the/Ni heterogeneous interface has excellent electrocatalytic hydrogen and oxygen evolution activity and stability in an alkaline solution, and has efficient and stable electrocatalytic full-hydrolytic performance. The invention adopts a two-step electrochemical method to prepare the catalyst, the preparation process is simple, the raw materials are low in price and easy to obtain, and the prepared catalyst has excellent electrolyzed water performance and can realize the application of actual alkaline electrolyzed water.
Description
Technical Field
The invention belongs to the technical field of electrochemical catalytic materials, and particularly relates to a nickel-based alkaline electrolyzed water catalyst with a co-doped combination heterostructure and a preparation method thereof.
Background
At present, good environment is the basis of survival, and sufficient energy is the premise of social development. The problems of environmental pollution and energy shortage faced by the present society are key problems restricting survival and development. Therefore, there is an urgent need to address the development of clean renewable energy sources. The hydrogen energy is used as a new energy source with zero carbon emission, sustainability, renewability and high energy density, and is the most environment-friendly clean energy source. Therefore, how to produce hydrogen energy in a low-cost, high-efficiency and pollution-free manner has become a hot research point.
Two half reactions of the electrolyzed water, namely the hydrogen evolution reaction of the cathode and the oxygen evolution reaction of the anode have the advantages of no carbon emission, sustainable development, high product purity and the like, and are widely concerned. Electrolysis of water requires the application of a certain voltage to drive the production of hydrogen and oxygen. In order to reduce energy consumption and improve energy conversion efficiency, the process needs a high-efficiency, low-cost, continuous and stable catalyst to reduce energy consumption, and further realizes the practical application of hydrogen production by water electrolysis. At present, the high-activity catalyst is still a noble metal-based catalyst such as platinum, ruthenium, iridium, rhodium and the like. However, it is expensive and has poor stability, which limits its large-scale application. Therefore, the electrocatalyst with low development cost, high catalytic activity and good stability is the key of the practical application of the hydrogen production by water electrolysis.
At present, many non-noble metal-based electrocatalysts with excellent performance, low price and good stability, such as Fe, Co, Ni and Mo-based electrocatalysts, have been developed. Particularly, Ni-based catalysts have been widely studied for their characteristics of good conductivity, high catalytic activity, low cost, availability, and environmental friendliness, but metallic nickel has not very good catalytic activity and stability. Therefore, various strategies have been developed to improve the catalytic activity and stability of nickel, such as metal compound synthesis, alloying, heteroelement doping, heterostructure construction, and the like. However, most of the nickel-based catalysts show only good electrocatalytic hydrogen or oxygen evolution performance due to different selectivity of catalytic reaction, and the water electrolysis efficiency is low.
Therefore, in order to realize efficient electrolysis of water, it is necessary to develop a bifunctional electrocatalyst having both excellent hydrogen evolution reaction and oxygen evolution reaction.
Through the above analysis, the problems and defects of the prior art are as follows: the prior nickel-based catalyst has poor catalytic activity and stability and low water electrolysis efficiency.
The difficulty in solving the above problems and defects is: how to synthesize the bifunctional catalyst with high catalytic activity and stable activity by the combined design of various strategies.
The significance of solving the problems and the defects is as follows: the development of a bifunctional electrocatalyst having both excellent hydrogen evolution reactions and oxygen evolution reactions enables efficient electrolysis of water.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a nickel-based alkaline electrolyzed water catalyst with a co-doped combination heterostructure and a preparation method thereof.
The invention is realized by the nickel-based alkaline electrolytic water catalyst of the co-doping combined heterostructure, which is Cu and Fe co-doped Ni (OH) with rich heterogeneous interface2a/Ni heterostructure alkaline electrolyzed water catalyst; physical properties: has rich heterogeneous interface; chemical characteristics: catalyzing alkaline electrolyzed water reaction;
the molecular formula of the catalyst is as follows: EO-Cu3-Fe2-Ni50/NF。
Another object of the present invention is to provide a preparation method of the co-doped nickel-based alkaline electrolytic water catalyst with a heterostructure, wherein the preparation method of the co-doped nickel-based alkaline electrolytic water catalyst with a heterostructure comprises:
cu, Fe co-doped Ni (OH) by two-step electrochemical method2And loading the/Ni heterostructure catalyst on a foam nickel substrate.
Further, the preparation method of the nickel-based alkaline electrolytic water catalyst of the co-doped combination heterostructure comprises the following steps:
step one, processing foamed nickel: soaking foamed nickel with a certain area in concentrated hydrochloric acid in a beaker, and carrying out ultrasonic treatment; cleaning the soaked and ultrasonically treated foamed nickel by using deionized water and ethanol, and drying;
step two, preparing Cu by electrochemical deposition3-Fe2-Ni50/NF: loading Cu and Fe co-doped Ni on a working electrode foamed nickel substrate by adopting a three-electrode system through an electrochemical deposition method to obtain Cu3-Fe2-Ni50/NF；
Step three, synthesizing EO-Cu by electrochemical oxidation3-Fe2-Ni50/NF: method for preparing Cu by cyclic voltammetry by adopting three-electrode system3-Fe2-Ni50and/NF is subjected to electrochemical oxidation to obtain the nickel-based alkaline electrolytic water catalyst with the co-doped combination heterostructure.
Further, in the step one, the area of the foamed nickel is 1 multiplied by 1cm2(ii) a The ultrasonic treatment time is 10 min; to remove the oxide layer on the surface of the foamed nickel.
Further, in step two, the three-electrode system comprises: in Hg/Hg2SO4And a carbon rod as a reference electrode and a counter electrode, respectively.
Further, in the second step, the electrochemical deposition is used for preparing Cu3-Fe2-Ni50the/NF comprises the following steps:
adding a proper amount of copper salt, iron salt and nickel salt into the buffer solution, and stirring for a period of time by ultrasonic waves to obtain transparent electrolyte;
under a certain voltage, metal ions are electrodeposited on a foamed nickel substrate from electrolyte in the form of copper and iron co-doped nickel metal nanoparticles, the foamed nickel substrate is taken out after standing for a period of time, and deionized water is used for washing the foamed nickel substrate to obtain Cu3-Fe2-Ni50/NF。
Further, the buffer solution is boric acid solution, and the concentration of the buffer solution is 0.5M; the method has the effects of inhibiting generation of hydroxide and improving the purity of the sample.
The nickel salt is nickel nitrate hexahydrate, and the concentration of the nickel salt is 0.5M; the function is to provide abundant nickel ions.
The copper salt is copper nitrate trihydrate, and the concentration of the copper salt is 0.03M; acting to provide a copper dopant.
The ferric salt is ferric nitrate nonahydrate, and the concentration of the ferric salt is 0.02M; acting to provide an iron dopant.
The voltage is-2 Vvs2SO4The method is used for reducing and depositing metal ions from an electrolyte to a foamed nickel substrate in the form of copper and iron co-doped nickel metal nanoparticles under negative voltage, and the electrodeposition time is 600 seconds.
Further, in step three, the three-electrode system includes: with Cu3-Fe2-Ni50the/NF is a working electrode, and the graphite electrode and the Hg/HgO are respectively a counter electrode and a reference electrode.
Further, in the third step, the electrochemical oxidation is used for synthesizing EO-Cu3-Fe2-Ni50the/NF comprises the following steps:
cu prepared by cyclic voltammetry3-Fe2-Ni50Soaking the NF in 1.0M alkaline solution, and performing 25 cycles at a sweep rate of 100mV/s in a voltage range of-0.675-0 Vvs. The function is to oxidize part of the metal to hydroxide, building up a heterostructure.
The invention also aims to provide application of the nickel-based alkaline electrolyzed water catalyst with the co-doped combined heterostructure in alkaline electrolyzed water.
By combining all the technical schemes, the invention has the advantages and positive effects that: the catalyst is an alkaline electrolytic water catalyst loaded on foamed nickel and is combined with Ni (OH) through Cu and Fe codoping2Construction of/Ni heterostructure, modulation of oxidation state of active metal center Ni and provision of abundant Ni (OH)2a/Ni heterogeneous interface, so that the excellent electrocatalytic precipitation is realized in an alkaline solutionHydrogen and oxygen evolution activity and stability, and has high-efficiency and stable electrocatalytic full-hydrolytic performance. The invention adopts a two-step electrochemical method to prepare the catalyst, synthesizes the heterostructure catalyst under the conditions of normal temperature and normal pressure, has simple preparation process, low price of raw materials and easy obtainment, and the prepared catalyst has excellent electrolyzed water performance and can realize the application of actual alkaline electrolyzed water.
According to the invention, the stability of copper and iron co-doped nickel hydroxide is improved, the heterogeneous interface of the catalyst is stabilized, and the electronic structure of the catalyst is optimized by co-doping, so that the catalytic activity and stability of the electro-catalytic hydrogen evolution of the catalyst are improved. Meanwhile, the oxidation state of the active metal center nickel is adjusted through codoping of Cu and Fe, and the oxygen production efficiency and catalytic activity of electrocatalytic oxygen evolution are improved. The invention utilizes Cu and Fe co-doped combination Ni (OH)2The construction of the/Ni heterostructure realizes the synthesis of the catalyst with excellent electrochemical hydrogen and oxygen evolution catalytic activity and stability, and realizes the application of the alkaline electrolyzed water with high efficiency and stability.
The invention synthesizes Cu and Fe co-doped Ni (OH) by utilizing a double strategy2The experimental result of the/Ni heterostructure electrocatalyst shows that the stability of copper and iron co-doped nickel hydroxide is improved, and the Ni (OH) of the catalyst is stabilized2The electronic structure of the catalyst is optimized by the aid of the/Ni heterogeneous interface and the co-doping, so that the catalytic activity and stability of the catalyst for electrocatalytic hydrogen evolution are improved. In addition, the Cu and Fe are codoped to adjust the oxidation state of the active metal center nickel, and the oxygen production efficiency and catalytic activity of the electrocatalytic oxygen evolution are improved. In conclusion, the invention utilizes Ni (OH) co-doped with Cu and Fe by a two-step electrochemical method2depositing/Ni heterostructure on foamed nickel to obtain EO-Cu3-Fe2-Ni50the/NF electrocatalyst can realize high-efficiency stable alkaline electrolyzed water.
Drawings
Fig. 1 is a flow chart of a preparation method of a nickel-based alkaline electrolytic water catalyst codoped with a combination heterostructure according to an embodiment of the invention.
Fig. 2 is an XRD spectrum of the nickel-based alkaline electrolyzed water catalyst co-doped with a bonding heterostructure provided by an embodiment of the present invention.
Fig. 3 is a scanning electron microscope image of the nickel-based alkaline electrolyzed water catalyst co-doped with the heterostructure provided by the embodiment of the present invention.
FIG. 4 is a high transmission electron microscope image of a nickel-based alkaline electrolyzed water catalyst co-doped with a heterostructure provided by an embodiment of the invention.
FIG. 5 is an X-ray photoelectron spectrum of the nickel-based alkaline electrolyzed water catalyst of the co-doped combined heterostructure provided by the embodiment of the invention.
FIG. 6 is a graph showing the electrocatalytic polarization of hydrogen evolution of the nickel-based alkaline electrolyzed water catalyst co-doped with the heterostructure provided by the embodiment of the invention.
FIG. 7 is a graph of cyclic voltammetry for electrocatalytic oxygen evolution of a nickel-based alkaline electrolyzed water catalyst co-doped with a combination heterostructure provided by an embodiment of the invention.
Fig. 8 is a nickel-based alkaline electrolyzed water catalyst alkaline electrolyzed water polarization graph of a co-doped bonding heterostructure provided by an embodiment of the invention.
FIG. 9 is a graph of stability test i-t curve of nickel-based alkaline electrolyzed water catalyst alkaline electrolyzed water co-doped with a combination heterostructure provided by an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Aiming at the problems in the prior art, the invention provides a nickel-based alkaline electrolyzed water catalyst codoped with a heterostructure and a preparation method thereof, and the invention is described in detail with reference to the attached drawings.
The nickel-based alkaline electrolytic water catalyst codoped with the heterostructure provided by the embodiment of the invention is Ni (OH) codoped with Cu and Fe2a/Ni heterostructure catalyst;
the molecular formula of the catalyst provided by the embodiment of the invention is as follows: EO-Cu3-Fe2-Ni50/NF。
The preparation method of the nickel-based alkaline electrolytic water catalyst with the co-doped combination heterostructure provided by the embodiment of the invention comprises the following steps:
cu, Fe co-doped Ni (OH) by two-step electrochemical method2And loading the/Ni heterostructure catalyst on a foam nickel substrate.
As shown in fig. 1, a preparation method of a nickel-based alkaline electrolytic water catalyst co-doped with a bonding heterostructure provided in an embodiment of the present invention includes the following steps:
s101, processing foamed nickel: mixing 1X 1cm2Soaking the foamed nickel by concentrated hydrochloric acid in a beaker, and carrying out ultrasonic treatment for 10 min; cleaning the soaked and ultrasonically treated foamed nickel by using deionized water and ethanol, and drying;
s102, preparing Cu by electrochemical deposition3-Fe2-Ni50/NF: in Hg/Hg2SO4And a carbon rod is respectively used as a reference electrode and a counter electrode, and Ni metal nano particles codoped with Cu and Fe are loaded on a working electrode foamed nickel substrate by an electrochemical deposition method to obtain Cu3-Fe2-Ni50/NF；
S103, synthesizing EO-Cu by electrochemical oxidation3-Fe2-Ni50/NF: with Cu3-Fe2-Ni50the/NF is a working electrode, the graphite electrode and the Hg/HgO are respectively a counter electrode and a reference electrode, and the prepared Cu is subjected to cyclic voltammetry3-Fe2-Ni50and/NF is subjected to electrochemical oxidation to obtain the nickel-based alkaline electrolytic water catalyst with the co-doped combination heterostructure.
The embodiment of the invention provides a method for preparing Cu by electrochemical deposition3-Fe2-Ni50the/NF comprises the following steps:
adding 0.5M nickel nitrate hexahydrate, 0.03M copper nitrate trihydrate and 0.02M iron nitrate nonahydrate into a boric acid solution with the concentration of 0.5M, and ultrasonically stirring for a period of time to obtain a transparent electrolyte;
at-2 Vvs2SO4At a voltage of (2), co-doping metal ions with copper and ironElectrodepositing nickel metal nanoparticles from the electrolyte onto a foamed nickel substrate, standing for a period of time, taking out, and washing with deionized water to obtain Cu3-Fe2-Ni50/NF。
The electrodeposition time provided by the embodiment of the invention is 600 seconds.
The electrochemical oxidation synthesis EO-Cu provided by the embodiment of the invention3-Fe2-Ni50the/NF comprises the following steps:
cu prepared by cyclic voltammetry3-Fe2-Ni50Soaking the NF in 1.0M alkaline solution, and performing 25 cycles at a sweep rate of 100mV/s in a voltage range of-0.675-0 Vvs.
The technical solution of the present invention is further described with reference to the following specific embodiments.
Example 1:
the invention provides a nickel-based alkaline electrolytic water catalyst codoped with a combined heterostructure, which is Ni (OH) codoped with Cu and Fe2the/Ni heterostructure catalyst was supported on the treated nickel foam by a two-step electrochemical process.
The invention provides a preparation method of the catalyst, which comprises the following steps:
(1) treating foamed nickel: putting foam nickel with a certain area in a beaker, adding concentrated hydrochloric acid, soaking and ultrasonically treating for a certain time, taking out, cleaning with a large amount of deionized water and ethanol, and drying.
(2) Electrochemical deposition of Cu3-Fe2-Ni50/NF: in Hg/Hg2SO4And the carbon rod is respectively used as a reference electrode and a counter electrode, and Cu and Fe co-doped Ni is loaded on the working electrode foamed nickel substrate by an electrochemical deposition method. Taking a buffer solution with a certain concentration and a certain amount of copper salt, iron salt and nickel salt as electrolyte, electrodepositing metal ions on a foamed nickel substrate from the electrolyte in the form of copper and iron co-doped nickel metal nanoparticles under a certain voltage, and taking out after a period of time.
(3) Electrochemical Oxidation (EO) synthesis of EO-Cu3-Fe2-Ni50/NF: the electrochemical oxidation was carried out by a three-electrode system using the catalyst obtained in step (2) as a working electrode, a graphite electrode and Hg/HgO as a counter electrode and a reference electrode, respectively. The process utilizes cyclic voltammetry to perform a certain number of cycles in an alkaline solution with a certain concentration and a certain voltage range and at a certain sweep rate.
The certain area in the step (1) is 1 multiplied by 1cm2The fixed time is 10 minutes.
The buffer solution in the step (2) is boric acid solution with the concentration of 0.5M, the nickel salt is nickel nitrate hexahydrate with the concentration of 0.5M, the copper salt is copper nitrate trihydrate with the concentration of 0.03M, the iron salt is ferric nitrate nonahydrate with the concentration of 0.02M, and the voltage is-2 Vvs2SO4The electrodeposition time was 600 seconds.
And (3) the alkaline solution is potassium hydroxide with the concentration of 1.0M, the voltage range is-0.675-0 Vvs. RHE, the sweeping speed is 100mV/s, and the circulation times are 25.
The nickel-based alkaline electrolytic water catalyst with the co-doped combination heterostructure manufactured by the invention has the application as an electrochemical alkaline electrolytic water catalyst.
FIG. 2 is an XRD pattern of the catalyst prepared in example 2, from which it can be seen that only Ni and Ni (OH)2The diffraction peak of (2) was found to be not a diffraction peak of Cu or Fe, and Ni/Ni (OH) co-doped with Cu or Fe was found to be present2The successful synthesis of the compound.
FIG. 3 is a scanning electron micrograph of the catalyst prepared according to example 2, from which it can be seen that the catalyst is nanoparticles having a diameter of about 300 nm.
FIG. 4 is a high power transmission electron micrograph of the catalyst prepared according to example 2; two kinds of lattice stripes can be seen, d 0.240nm attributed to Ni (OH)2(101) And d ═ 0.21nm was assigned to Ni (111). From this, Ni (OH)2Successful synthesis of/Ni and a rich heterointerface can be seen.
FIG. 5 is an X-ray photoelectron spectrum of the catalyst prepared in example 2; from the figureNi is mainly divalent, as is known from Ni (OH)2Exists in the form of (1); cu is present in the catalyst predominantly in the zeroth and divalent states, Fe is present predominantly in the zeroth and trivalent states, indicating successful doping of Cu and Fe.
FIG. 6 is an electrocatalytic hydrogen evolution polarization curve for the catalyst prepared according to example 2; as can be seen from the graph, the current density was 10mA/cm2The overpotential of (3) is 25mV at the current density of (3). The comparative performance is superior to most of the reported hydrogen evolution electrocatalysts. Indicating electrochemical Oxidation to build Ni (OH)2the/Ni heterogeneous interface has great promotion on hydrogen evolution performance, and the regulation of the Cu and Fe doping on the electronic structure of the catalyst is also beneficial to further promotion of the performance.
FIG. 7 is an electrocatalytic oxygen evolution cyclic voltammogram of the catalyst prepared as in example 2. As can be seen from the graph, the current density was 10mA/cm2The overpotential of (2) was 202mV at the current density of (1). The comparative performance is better than most oxygen evolution electrocatalysts. And the oxidation potential of the catalyst is increased along with the doping of Cu and Fe metal elements, which means that the oxidation state of a metal active center is reduced along with the doping of the Cu and Fe metal elements in the oxygen evolution reaction process, so that the energy barrier of the oxygen evolution reaction is reduced, the oxygen generation efficiency is improved, and the catalytic activity is improved.
FIG. 8 is an alkaline electrolyzed water polarization curve of the catalyst prepared in example 2; from the figure, it can be seen that Ni (OH) is bonded by codoping Cu and Fe2The catalyst constructed by the/Ni heterostructure shows excellent alkaline electrolyzed water performance. At 10mA/cm2The voltage is only 1.439V at the operating current density of (a).
FIG. 9 is a stability test i-t curve for alkaline electrolyzed water of the catalyst prepared in example 2; as can be seen from the figure, at 10mA/cm2Can continue to operate stably for at least 36 hours, indicating that the catalyst has excellent alkaline electrolyzed water stability.
The invention is characterized by XRD, XPS and HRTEM, and can know that EO-Cu3-Fe2-Ni50the/NF sample is Cu, Fe co-doped Ni (OH)2Composition of/Ni heterostructure, Ni (OH)2By electrochemical oxidation of NiAnd (5) growing the line. Electrochemical tests show that the catalyst has excellent and stable alkaline electrolyzed water performance.
Example 2:
the preparation method of the nickel-based alkaline electrolytic water catalyst with the co-doped combination heterostructure comprises the following steps: firstly, 1.0cm2The foamed nickel is placed in a beaker, concentrated hydrochloric acid is added, ultrasonic treatment is carried out for 10 minutes, and the foamed nickel is taken out, cleaned by a large amount of deionized water and ethanol and dried. Then Ni is loaded on the foamed nickel substrate of the working electrode by an electrochemical deposition method to Hg/Hg2SO4And a carbon rod as a reference electrode and a counter electrode respectively, 0.03M of copper nitrate trihydrate, 0.005M of ferric nitrate nonahydrate, 0.5M of boric acid buffer solution and 0.5M of nickel nitrate hexahydrate are used as electrolyte, and the electrolyte is adjusted to-2 Vvs2SO4Under the voltage of (2), Cu, Fe and Ni ions are electrodeposited on the foamed nickel substrate from the electrolyte in the form of Cu and Fe co-doped Ni metal nano particles, and are taken out after 600 seconds. And finally, carrying out electrochemical oxidation through a three-electrode system, wherein the obtained catalyst is used as a working electrode, and a graphite electrode and Hg/HgO are respectively used as a counter electrode and a reference electrode. The electrochemical oxidation is carried out by cyclic voltammetry within the voltage range of-0.675 to 0Vvs.RHE in 1.0M potassium hydroxide solution at the sweep rate of 100mV/s for 25 cycles.
Example 3:
the preparation method of the nickel-based alkaline electrolytic water catalyst with the co-doped combination heterostructure comprises the following steps: firstly, 1.0cm2The foamed nickel is placed in a beaker, concentrated hydrochloric acid is added, ultrasonic treatment is carried out for 10 minutes, and the foamed nickel is taken out, cleaned by a large amount of deionized water and ethanol and dried. Then Ni is loaded on the foamed nickel substrate of the working electrode by an electrochemical deposition method to Hg/Hg2SO4And a carbon rod as a reference electrode and a counter electrode respectively, 0.03M of copper nitrate trihydrate, 0.02M of ferric nitrate nonahydrate, 0.5M of boric acid buffer solution and 0.5M of nickel nitrate hexahydrate are used as electrolyte, and the electrolyte is at-2.5 Vvs2SO4Under the voltage of (2), Cu, Fe and Ni ions are electrodeposited on a foamed nickel substrate from an electrolyte in the form of Cu and Fe co-doped Ni metal nano particles for 600 secondsAnd then taking out. And finally, carrying out electrochemical oxidation through a three-electrode system, wherein the obtained catalyst is used as a working electrode, and a graphite electrode and Hg/HgO are respectively used as a counter electrode and a reference electrode. The electrochemical oxidation is carried out by cyclic voltammetry within the voltage range of-0.675 to 0Vvs.RHE in 1.0M potassium hydroxide solution at the sweep rate of 100mV/s for 25 cycles.
Example 4:
the preparation method of the nickel-based alkaline electrolytic water catalyst with the co-doped combination heterostructure comprises the following steps: firstly, 1.0cm2The foamed nickel is placed in a beaker, concentrated hydrochloric acid is added, ultrasonic treatment is carried out for 10 minutes, and the foamed nickel is taken out, cleaned by a large amount of deionized water and ethanol and dried. Then Ni is loaded on the foamed nickel substrate of the working electrode by an electrochemical deposition method to Hg/Hg2SO4And a carbon rod as a reference electrode and a counter electrode respectively, 0.03M of copper nitrate trihydrate, 0.03M of ferric nitrate nonahydrate, 0.5M of boric acid buffer solution and 0.5M of nickel nitrate hexahydrate are used as electrolyte, and the electrolyte is adjusted to-2 Vvs2SO4Under the voltage of (2), Cu, Fe and Ni ions are electrodeposited on the foamed nickel substrate from the electrolyte in the form of Cu and Fe co-doped Ni metal nano particles, and are taken out after 600 seconds. And finally, carrying out electrochemical oxidation through a three-electrode system, wherein the obtained catalyst is used as a working electrode, and a graphite electrode and Hg/HgO are respectively used as a counter electrode and a reference electrode. The electrochemical oxidation is carried out by cyclic voltammetry within the voltage range of-0.675 to 0Vvs.RHE in 1.0M potassium hydroxide solution at the sweep rate of 50mV/s for 30 cycles.
In examples 1 to 4 of the present invention, the area of the catalyst working electrode was 1.0cm2In order to make the data obtained by the electrochemical tests comparable, the following examples were all subjected to electrochemical tests using CHI660E electrochemical workstation from Chensinensis instruments. The test conditions were as follows: the graphite electrode is used as a counter electrode, the Hg/HgO electrode is used as a reference electrode, and the graphite electrode and the catalyst form a three-electrode system together, and the electrolyte is a 1.0MKOH aqueous solution.
The above description is only for the purpose of illustrating the present invention and the appended claims are not to be construed as limiting the scope of the invention, which is intended to cover all modifications, equivalents and improvements that are within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The nickel-based alkaline electrolytic water catalyst codoped with the combination heterostructure is characterized in that the nickel-based alkaline electrolytic water catalyst codoped with the combination heterostructure is Cu and Fe codoped Ni (OH)2a/Ni heterostructure catalyst;
the molecular formula of the catalyst is as follows: EO-Cu3-Fe2-Ni50/NF。
2. The preparation method of the nickel-based alkaline electrolytic water catalyst codoped with the combination heterostructure of claim 1, wherein the preparation method of the nickel-based alkaline electrolytic water catalyst codoped with the combination heterostructure comprises the following steps:
cu, Fe co-doped Ni (OH) by two-step electrochemical method2And loading the/Ni heterostructure catalyst on a foam nickel substrate.
3. The method for preparing the nickel-based alkaline electrolytic water catalyst co-doped with the bonding heterostructure of claim 2, wherein the method for preparing the nickel-based alkaline electrolytic water catalyst co-doped with the bonding heterostructure comprises the following steps:
step one, processing foamed nickel: soaking foamed nickel with a certain area in concentrated hydrochloric acid in a beaker, and carrying out ultrasonic treatment; cleaning the soaked and ultrasonically treated foamed nickel by using deionized water and ethanol, and drying;
step two, preparing Cu by electrochemical deposition3-Fe2-Ni50/NF: loading Cu and Fe co-doped Ni on a working electrode foamed nickel substrate by adopting a three-electrode system through an electrochemical deposition method to obtain Cu3-Fe2-Ni50/NF；
Step three, synthesizing EO-Cu by electrochemical oxidation3-Fe2-Ni50/NF: method for preparing Cu by cyclic voltammetry by adopting three-electrode system3-Fe2-Ni50and/NF is subjected to electrochemical oxidation to obtain the nickel-based alkaline electrolytic water catalyst with the co-doped combination heterostructure.
4. The method for preparing the nickel-based alkaline electrolytic water catalyst codoped with a heterostructure of claim 3, wherein in the first step, the area of the foamed nickel is 1 x 1cm2(ii) a The sonication time was 10 minutes.
5. The method for preparing the nickel-based alkaline electrolytic water catalyst codoped with the heterostructure of claim 3, wherein in the second step, the three-electrode system comprises: in Hg/Hg2SO4And a carbon rod as a reference electrode and a counter electrode, respectively.
6. The method for preparing the nickel-based alkaline electrolytic water catalyst codoped with a heterostructure of claim 3, wherein in the second step, the electrochemical deposition is used for preparing Cu3-Fe2-Ni50the/NF comprises the following steps:
adding a proper amount of copper salt, iron salt and nickel salt into the buffer solution, and stirring for a period of time by ultrasonic waves to obtain transparent electrolyte;
under a certain voltage, metal ions are electrodeposited on a foamed nickel substrate from electrolyte in the form of copper and iron co-doped nickel metal nanoparticles, the foamed nickel substrate is taken out after standing for a period of time, and deionized water is used for washing the foamed nickel substrate to obtain Cu3-Fe2-Ni50/NF。
7. The method for preparing the nickel-based alkaline electrolytic water catalyst co-doped with the heterostructure of claim 6, wherein the buffer solution is a boric acid solution, and the concentration of the buffer solution is 0.5M;
the nickel salt is nickel nitrate hexahydrate, and the concentration of the nickel salt is 0.5M;
the copper salt is copper nitrate trihydrate, and the concentration of the copper salt is 0.03M;
the ferric salt is ferric nitrate nonahydrate, and the concentration of the ferric salt is 0.02M;
the voltage is-2V vs. Hg/Hg2SO4The electrodeposition time was 600 seconds.
8. The method for preparing the nickel-based alkaline electrolytic water catalyst co-doped with the heterostructure of claim 3, wherein in step three, the three-electrode system comprises: with Cu3-Fe2-Ni50the/NF is a working electrode, and the graphite electrode and the Hg/HgO are respectively a counter electrode and a reference electrode.
9. The method for preparing the nickel-based alkaline electrolytic water catalyst codoped with the heterostructure of claim 3, wherein in step three, the electrochemical oxidation is performed to synthesize EO-Cu3-Fe2-Ni50the/NF comprises the following steps:
cu prepared by cyclic voltammetry3-Fe2-Ni50Soaking the NF in 1.0M alkaline solution, and performing 25 cycles at a sweep rate of 100mV/s in a voltage range of-0.675-0 Vvs.
10. The nickel-based alkaline electrolyzed water catalyst codoped with a combined heterostructure as claimed in claim 1 can be applied to alkaline electrolyzed water.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114737215A (en) * | 2022-03-31 | 2022-07-12 | 福建工程学院 | Preparation method of nickel-tungsten composite electrode and application of nickel-tungsten composite electrode in electrocatalytic oxidation |
| CN114990622A (en) * | 2022-06-02 | 2022-09-02 | 蚌埠学院 | Preparation method of sea urchin-shaped iron-doped nickel hydroxide oxygen evolution catalyst |
| CN115404509A (en) * | 2022-08-09 | 2022-11-29 | 电子科技大学 | Self-repairing oxygen evolution catalyst and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108823625A (en) * | 2018-07-02 | 2018-11-16 | 中南大学 | A kind of complex metal hydroxide and its preparation method and application |
| CN110468427A (en) * | 2019-07-24 | 2019-11-19 | 天津大学 | A kind of self-supporting doping metals hydroxide nano plate electrode material, preparation method and the usage |
| CN110773173A (en) * | 2019-11-28 | 2020-02-11 | 郑州大学 | Bifunctional catalyst β -Ni (OH) 2/NF, preparation method and application thereof |
| CN111905744A (en) * | 2020-07-23 | 2020-11-10 | 安徽工业大学 | Nickel-iron hydroxide composite material, catalyst, preparation method and application |
| CN112647092A (en) * | 2020-12-18 | 2021-04-13 | 江苏大学 | Supported nickel-based composite hydrogen evolution catalyst and preparation method and application thereof |
| CN112808274A (en) * | 2019-10-29 | 2021-05-18 | 湖南师范大学 | High-performance iron-doped nickel or cobalt-based amorphous oxyhydroxide catalyst prepared by room temperature method and research on efficient water electrolysis hydrogen production thereof |
| CN113106488A (en) * | 2021-03-25 | 2021-07-13 | 中山大学 | Preparation method of iron-doped nickel sulfide oxygen evolution electrocatalyst |
-
2021
- 2021-11-19 CN CN202111409070.9A patent/CN113957456A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108823625A (en) * | 2018-07-02 | 2018-11-16 | 中南大学 | A kind of complex metal hydroxide and its preparation method and application |
| CN110468427A (en) * | 2019-07-24 | 2019-11-19 | 天津大学 | A kind of self-supporting doping metals hydroxide nano plate electrode material, preparation method and the usage |
| CN112808274A (en) * | 2019-10-29 | 2021-05-18 | 湖南师范大学 | High-performance iron-doped nickel or cobalt-based amorphous oxyhydroxide catalyst prepared by room temperature method and research on efficient water electrolysis hydrogen production thereof |
| CN110773173A (en) * | 2019-11-28 | 2020-02-11 | 郑州大学 | Bifunctional catalyst β -Ni (OH) 2/NF, preparation method and application thereof |
| CN111905744A (en) * | 2020-07-23 | 2020-11-10 | 安徽工业大学 | Nickel-iron hydroxide composite material, catalyst, preparation method and application |
| CN112647092A (en) * | 2020-12-18 | 2021-04-13 | 江苏大学 | Supported nickel-based composite hydrogen evolution catalyst and preparation method and application thereof |
| CN113106488A (en) * | 2021-03-25 | 2021-07-13 | 中山大学 | Preparation method of iron-doped nickel sulfide oxygen evolution electrocatalyst |
Non-Patent Citations (1)
| Title |
|---|
| CHIDANAND HEGDE等: "Cu- and Fe-Codoped Ni Porous Networks as an Active Electrocatalyst for Hydrogen Evolution in Alkaline Medium", 《ACS APPL. MATER. INTERFACES》, vol. 12, pages 2380 - 2389 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114737215A (en) * | 2022-03-31 | 2022-07-12 | 福建工程学院 | Preparation method of nickel-tungsten composite electrode and application of nickel-tungsten composite electrode in electrocatalytic oxidation |
| CN114737215B (en) * | 2022-03-31 | 2023-11-14 | 福建工程学院 | Preparation method of nickel-tungsten composite electrode and application of nickel-tungsten composite electrode in electrocatalytic oxidation |
| CN114990622A (en) * | 2022-06-02 | 2022-09-02 | 蚌埠学院 | Preparation method of sea urchin-shaped iron-doped nickel hydroxide oxygen evolution catalyst |
| CN115404509A (en) * | 2022-08-09 | 2022-11-29 | 电子科技大学 | Self-repairing oxygen evolution catalyst and preparation method and application thereof |
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