CN113046782A - Preparation of foam nickel-loaded cuprous oxide octahedral catalyst and application of foam nickel-loaded cuprous oxide octahedral catalyst in seawater electrolysis hydrogen production - Google Patents
Preparation of foam nickel-loaded cuprous oxide octahedral catalyst and application of foam nickel-loaded cuprous oxide octahedral catalyst in seawater electrolysis hydrogen production Download PDFInfo
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- CN113046782A CN113046782A CN202110258245.4A CN202110258245A CN113046782A CN 113046782 A CN113046782 A CN 113046782A CN 202110258245 A CN202110258245 A CN 202110258245A CN 113046782 A CN113046782 A CN 113046782A
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- cuprous oxide
- foam nickel
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to the technical field of hydrogen production by hydrolysis, and particularly relates to a preparation method of a foam nickel-loaded cuprous oxide octahedral catalyst and application of the foam nickel-loaded cuprous oxide octahedral catalyst in hydrogen production by seawater electrolysis4Taking out the solution, washing, exposing in air for a period of time, and finally drying to obtain the product. The foam nickel supported cuprous oxide octahedron catalyst can be carried out under seawater electrolyte, solves partial problems of seawater hydrogen evolution, is economical and environment-friendly, can meet the requirement of replacing noble metals, and has the advantages of high porosity, high stability, self-support and the like.
Description
Technical Field
The invention belongs to the technical field of hydrogen production by hydrolysis, and particularly relates to a preparation method of a nickel foam loaded cuprous oxide octahedron catalyst and application of the nickel foam loaded cuprous oxide octahedron catalyst in seawater electrolysis hydrogen production.
Background
The development can be sustained in dealing with environmental problems such as climate change and the like caused by the over use of global energy, particularly fossil energyA continuous, clean, efficient energy source is an effective way. Hydrogen (H)2) Due to its high weight energy density (142MJ kg)-1) Wide source, zero carbon emission and the like, and is considered to be a promising alternative energy carrier for the traditional fossil fuel. Among them, electrochemical hydrolysis is a promising method for producing hydrogen energy, and the method is simple and environment-friendly, and has high yield and high product purity. Electrochemical hydrolysis involves two half-reactions, the Hydrogen Evolution Reaction (HER) at the cathode and the Oxygen Evolution Reaction (OER) at the anode. However, in commercial water electrolyzers, the cell voltage (1.8-2.0V) required to drive hydrolysis is much greater than the theoretical value (1.23V), resulting in high water electrolyzer power consumption. Although catalytic water cracking using noble metals Ru and Pt can solve the problem of high energy consumption to some extent, they are expensive, scarce in quantity and poor in durability, resulting in limitation of their large-scale application. Therefore, the development of abundant and well coupled OER and HER catalysts is essential to achieve efficient water splitting.
The transition metal has unique electronic structure and chemical characteristics, is rich in content and easy to obtain, and is expected to be applied to catalytic cracking of water after the OER and HER performances are improved by structural regulation. However, most of the currently prepared transition metal electrocatalysis systems are operated in high-purity distilled water electrolytes containing acids, alkalis or buffers, and there are few reports of electrocatalysis water cracking by using seawater, mainly because hundreds of different impurities contained in natural seawater can cause catalyst poisoning and unknown side reactions. However, about 97% of water resources available on earth are seawater, so that the development of a transition metal catalytic system capable of electrically catalyzing seawater to generate hydrogen becomes a hot point of research in recent years.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a foam nickel-loaded cuprous oxide octahedron catalyst, and the prepared catalyst has the potential of being applied to seawater electrolysis hydrogen production.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of a foam nickel-loaded cuprous oxide octahedron catalyst, which comprises the following steps:
s1, cleaning and drying the foamed nickel;
s2, quickly immersing the processed foamed nickel into warm CuSO4Taking out the solution, washing the solution, exposing the washed solution in the air for a period of time, and finally drying the washed solution to obtain the foam nickel supported cuprous oxide octahedral catalyst (marked as octahedral Cu)2O/NF)。
The octahedron Cu is prepared by adopting an in-situ process2The O/NF is used as an integrated electrode, can effectively overcome the defect that nano particles are used as an electrode material, and directly uses a self-supporting material as the electrode, so that the O/NF has the advantages of enlarging electrochemical surface area, accelerating electrolyte diffusion, facilitating air bubbles to migrate from the surface of a catalyst and the like, thereby improving the performance of the electrocatalyst. Furthermore, the nanostructured catalyst Cu grown in situ on the integrated electrode2The research shows that the Cu of the invention can effectively improve the electron conversion because of better interface contact and no adhesive property2The O/NF has good hydrogen evolution performance in simulated seawater and is expected to be applied to the seawater electrolysis hydrogen production.
Preferably, the CuSO4The concentration of the solution is 0.5M-1.5M. Specifically, the CuSO4The concentration of the solution was 1M.
Preferably, the nickel foam is in CuSO4The soaking time in the solution is 7-15 s. Specifically, the nickel foam is prepared in CuSO4The soaking time in the solution was 10 s.
Preferably, the CuSO4The temperature of the solution is 70-90 ℃. Specifically, the CuSO4The temperature of the solution was 80 ℃.
Preferably, the exposure time in air is between 0.5h and 1.5 h. Specifically, the exposure time in air was 1 h.
Preferably, the cleaning in step S1 is ultrasonic cleaning with hydrochloric acid, acetone, ethanol (typically absolute ethanol) and water, respectively.
Furthermore, the power of ultrasonic cleaning is 300W-400W, and the time is 20min-40 min. Specifically, the power of ultrasonic cleaning is 360W, and the time is 30 min.
The invention also provides the foam nickel-loaded cuprous oxide octahedral catalyst prepared by the preparation method.
The invention also provides application of the foam nickel-loaded cuprous oxide octahedron catalyst in seawater electrolysis hydrogen production.
Compared with the prior art, the invention has the beneficial effects that:
the invention prepares a foam nickel-supported cuprous oxide octahedral catalyst by an in-situ process, namely, the cleaned foam nickel is quickly immersed into warm CuSO4Taking out the solution, washing, exposing in air for a period of time, and finally drying to prepare the product. The foam nickel supported cuprous oxide octahedron catalyst prepared by the invention can be carried out under seawater electrolyte, solves partial problems of seawater hydrogen evolution, is economic and environment-friendly, can meet the requirement of replacing noble metals, and has the advantages of high porosity, high stability, self-support and the like.
Drawings
FIG. 1 is Cu2Scanning electron microscopy images of O/NF;
FIG. 2 is Cu2Linear sweep voltammogram of O/NF in alkaline electrolyte for hydrogen evolution (A) and oxygen evolution (B) (potential: E/V on abscissa, current density: j/mA + cm on ordinate)2)；
FIG. 3 is Cu2Linear sweep voltammogram of O/NF in alkaline electrolyte for hydrogen evolution (A) and oxygen evolution (B) (potential: E/V on abscissa, current density: j/mA on ordinate)+cm2)；
FIG. 4 is Cu2Hydrogen evolution linear scanning voltammogram of O/NF in simulated seawater (the abscissa is potential: E/V, and the ordinate is current density: j/mA)+cm2)。
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
Example 1 preparation of foamed nickel supported cuprous oxide octahedral catalyst
(1) Ultrasonically cleaning foamed nickel (Ni foam, NF) with the size of 2cm multiplied by 3cm multiplied by 2mm for 30min under the power of 360W by 6M hydrochloric acid, acetone, absolute ethyl alcohol and water respectively, and drying at the temperature of 60 ℃ in vacuum;
(2) immersing the treated foam nickel into 1M CuSO at 80 DEG C4Generating cuprous oxide on the surface of the carrier by a displacement method in the solution for 10s, taking out the foamed nickel by a pair of tweezers, washing thoroughly by deionized water (washing till the last washing water turns colorless), exposing in the air for 1h, and drying at 60 ℃ to obtain the octahedral Cu2O/NF, i.e., a nickel foam supported cuprous oxide octahedral catalyst.
For the prepared Cu2The O/NF was observed by scanning electron microscopy using a JEOL JSM-IT200A instrument. As shown in the surface topography at 10 μm and 1 μm magnification of fig. 1, it is evident that the cuprous oxide on the nickel foam is octahedral. At the same time, for Cu2The O/NF was observed by X-ray electron diffraction, and the instrument model used was C.ultima IV. As shown in FIG. 2, according to the comparison of standard cards, Cu can be compared with2O and foam nickel pair, the sample was proven to be Cu on foam nickel2And (4) O crystals.
Example 2 preparation of foamed nickel supported cuprous oxide octahedral catalyst
(1) Ultrasonically cleaning foamed nickel (Ni foam, NF) with the size of 2cm multiplied by 3cm multiplied by 2mm for 40min under the power of 300W by hydrochloric acid, acetone, absolute ethyl alcohol and water respectively, and drying at the temperature of 60 ℃ in vacuum;
(2) immersing the treated foam nickel into 0.5M CuSO at 70 DEG C4In solution for 20s, by displacement on the support surfaceCuprous oxide is generated on the surface, then the foam nickel is taken out by a pair of tweezers, and is thoroughly washed by deionized water (until the last washing water turns to be colorless), exposed in the air for 0.5h, and dried at 60 ℃ to obtain octahedral Cu2O/NF。
Example 3 preparation of foamed nickel supported cuprous oxide octahedral catalyst
(1) Ultrasonically cleaning foamed nickel (Ni foam, NF) with the size of 2cm multiplied by 3cm multiplied by 2mm for 20min under the power of 400W by hydrochloric acid, acetone, absolute ethyl alcohol and water respectively, and drying at the temperature of 60 ℃ in vacuum;
(2) immersing the treated foamed nickel into 1.5M CuSO at 90 DEG C4Generating cuprous oxide on the surface of the carrier by a displacement method for 7s in the solution, taking out the foamed nickel by a pair of tweezers, washing thoroughly by deionized water (washing till the last washing water turns colorless), exposing in the air for 1.5h, and drying at 60 ℃ to obtain the octahedral Cu2O/NF。
Experimental example 1 electrochemical test
The electrochemical test was carried out in a three-electrode system (test instrument AUTOLAB model AUT88171), the test instrument AUTOLAB model AUT88171, the electrolyte was simulated seawater (1M KOH +0.5M NaCl) or alkaline electrolyte (1M KOH), the reference electrode was Hg/HgO, the counter electrode was platinum sheet electrode, and the working electrode was octahedral Cu prepared in example 12O/NF, after the circuit connection is checked to be correct, setting a program, selecting Linear sweep voltammetry potential to perform hydrogen evolution test, setting the potential range to be-0.97 to-1.77V, and the scanning rate to be 0.005V/s, and drawing a Linear Sweep Voltammetry (LSV) curve graph.
Cu as shown in FIG. 32The patterns of (A) HER and (B) OER of O/NF in 1M KOH show that Cu2The O/NF has certain hydrogen evolution and oxygen evolution performances in the 1M KOH alkaline electrolyte. Cu as shown in FIG. 42The HER diagram of O/NF in simulated seawater (1M KOH +0.5M NaCl) shows that Cu2The O/NF has good hydrogen evolution performance in simulated seawater.
Furthermore, octahedral Cu prepared in examples 2 and 32The electrochemical test results for O/NF were the same or similar to those of example 1.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and still fall within the scope of the invention.
Claims (9)
1. The preparation method of the foam nickel supported cuprous oxide octahedron catalyst is characterized by comprising the following steps of:
s1, cleaning and drying the foamed nickel;
s2, quickly immersing the processed foamed nickel into warm CuSO4And taking out the solution, washing the solution, exposing the washed solution in the air for a period of time, and finally drying the solution to obtain the foam nickel supported cuprous oxide octahedral catalyst.
2. The method for preparing the foam nickel supported cuprous oxide octahedral catalyst according to claim 1, wherein the CuSO is4The concentration of the solution is 0.5M-1.5M.
3. The method for preparing the foam nickel supported cuprous oxide octahedral catalyst according to claim 1, wherein the foam nickel is in CuSO4The soaking time in the solution is 7-15 s.
4. The method for preparing the foam nickel supported cuprous oxide octahedral catalyst according to claim 1, wherein the CuSO is4The temperature of the solution is 70-90 ℃.
5. The preparation method of the foam nickel supported cuprous oxide octahedral catalyst according to claim 1, wherein the exposure time in air is 0.5h-1.5 h.
6. The preparation method of the foam nickel supported cuprous oxide octahedral catalyst according to claim 1, wherein the cleaning in step S1 is ultrasonic cleaning with hydrochloric acid, acetone, ethanol and water respectively.
7. The preparation method of the foam nickel supported cuprous oxide octahedral catalyst according to claim 7, wherein the power of ultrasonic cleaning is 300W-400W, and the time is 20min-40 min.
8. The foamed nickel supported cuprous oxide octahedral catalyst prepared by the preparation method of any one of claims 1 to 7.
9. The use of the foamed nickel supported cuprous oxide octahedral catalyst of claim 8 in the electrolysis of seawater to produce hydrogen.
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| US20160348256A1 (en) * | 2014-01-17 | 2016-12-01 | The Board Of Regents Of The University Of Texas System | Photoelectrochemical devices, methods, and systems with a cupric oxide/cuprous oxide coated electrode |
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| US20160348256A1 (en) * | 2014-01-17 | 2016-12-01 | The Board Of Regents Of The University Of Texas System | Photoelectrochemical devices, methods, and systems with a cupric oxide/cuprous oxide coated electrode |
| CN104911629A (en) * | 2015-06-29 | 2015-09-16 | 江苏大学 | Synthesis method of composite electrode |
| CN108786794A (en) * | 2017-04-28 | 2018-11-13 | 南京理工大学 | A kind of recyclable electrical enhanced photocatalysis agent and its preparation method and application |
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