CN115786964A - Cobalt-based spinel Cu 0.7 Co 2.3 O 4 Electrocatalyst and preparation method and application thereof - Google Patents
Cobalt-based spinel Cu 0.7 Co 2.3 O 4 Electrocatalyst and preparation method and application thereof Download PDFInfo
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- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 24
- 239000011029 spinel Substances 0.000 title claims abstract description 24
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 17
- 239000010941 cobalt Substances 0.000 title claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- 239000010949 copper Substances 0.000 claims abstract description 62
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 15
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 13
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- 239000000243 solution Substances 0.000 claims description 9
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- 239000012535 impurity Substances 0.000 claims description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 6
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
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- 239000010439 graphite Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 claims description 4
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- STXKJSYMVDTOSJ-UHFFFAOYSA-M chlorocopper hexahydrate Chemical group [Cu]Cl.O.O.O.O.O.O STXKJSYMVDTOSJ-UHFFFAOYSA-M 0.000 claims description 2
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 2
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Images
Abstract
The invention relates to cobalt-based spinel Cu 0.7 Co 2.3 O 4 The preparation method comprises the following steps of putting a pretreated foamy copper carrier into a solution dissolved with cobalt salt, copper salt, urea and ammonium fluoride, and then growing a basic cobalt carbonate copper precursor on a foamy copper substrate by a hydrothermal method; after drying, calcining to obtain Cu which grows on the foam copper substrate and is uniformly distributed 0.7 Co 2.3 O 4 An electrocatalyst. The catalyst shows excellent catalytic activity and stability in the application of electrically oxidizing glycerol into formate, and only 1.37V (vs. RHE) is needed to realize the effect of reaching 400 mA-cm ‑2 Industrial grade current density ofAnd the electrocatalytic performance is not attenuated after stable circulation for 60 hours, and the Faraday efficiency of the formate reaches more than 80%. The catalyst has the advantages of simple synthesis process, low cost and excellent catalytic performance, and shows good application prospect in the industry of producing formate by electrooxidation of glycerol.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and relates to cobalt-based spinel Cu 0.7 Co 2.3 O 4 A preparation method of the electrocatalyst and application of the electrocatalyst in realizing high-efficiency electrocatalytic oxidation of glycerol into formic acid.
Background
The method for effectively converting micromolecular organic matters into high-value fine chemicals by utilizing an electro-catalytic oxidation technology is one of novel energy processing technologies for realizing sustainable green development. Under normal temperature and pressure, the technology can selectively convert small molecular organic matters into various high value-added chemical products, such as methanol, formic acid, ethylene, acetone and the like. Meanwhile, the electrocatalysis energy conversion technology has the advantages of mild reaction conditions, environmental friendliness, high energy utilization rate and the like. Under the background that the power generation cost of renewable energy sources such as solar energy, wind energy, water energy and the like is reduced year by year, the small molecular organic electro-catalytic conversion technology has great development potential. The glycerol is used as an industrial micromolecule byproduct with serious surplus of capacity, the price is low, the raw material source is rich, and the formic acid is used as an important raw material in industrial production, is a precursor of various chemical products, is an anode material of a formic acid fuel cell and an excellent hydrogen storage material, and has higher economic value. Therefore, compared with the method for producing hydrogen and oxygen by electrolyzing water, the method for producing hydrogen by introducing the small molecular organic matters into the electrolyte through coupling can greatly reduce the power consumption and simultaneously produce and obtain fine chemicals with higher added values than oxygen.
The transition metal oxide is a kind of electrocatalytic oxidation catalyst which is common at the present stage, and has the advantages of high earth abundance, low cost, wide source and the like compared with a noble metal oxide catalyst. At present, researchers have preliminarily researched glycerol oxidation, but most of the researchers use precious metals as raw materials, so that the production cost is high, and meanwhile, the current density and the stability required by the catalyst have great promotion space. Therefore, the construction of a catalyst with low cost, large current density and long-term stability is of great significance. Among many metal oxides, spinel oxides have unique electronic structures and charge distributions, and exhibit more excellent performance for the electrooxidation of glycerol. Meanwhile, in the multi-metal oxide, the synergistic effect among multiple metals also greatly helps to improve the catalytic performance.
Based on this, the selection of appropriate transition metal elements, the development and design of catalysts with low cost, high catalytic performance and long-term stability are one of the keys for promoting the electrooxidation of glycerol to realize industrial application.
Disclosure of Invention
In view of the above, the invention provides a cobalt-based spinel Cu with low cost and simple operation aiming at the defects existing in the prior art 0.7 Co 2.3 O 4 The preparation method of the electrocatalyst is used in the electrocatalytic oxidation of the glycerol, the Faraday efficiency exceeds 80 percent, and the industrial-grade current density (400 mA-cm) can be achieved in a three-electrode system at lower voltage -2 ) The required operating voltage is much lower than for the OER reaction. Meanwhile, the method has the advantages of simple preparation, simple and convenient operation and high energy utilization rate.
It is noted that the cobalt-based spinel Cu prepared by the invention 0.7 Co 2.3 O 4 The electrocatalyst has a special sea urchin-shaped appearance, which is beneficial to the full contact between the catalyst and electrolyte, and the spines on the sea urchin-shaped appearance can expose more catalytic active sites, so that the catalytic activity of glycerol oxidation is increased.
More importantly, the introduction of copper ions and the migration in the crystal adjust the electronic structure in the crystal and optimize the intrinsic catalytic activity of the catalyst.
In order to achieve the above purpose, the invention provides the following technical scheme:
cobalt-based spinel Cu 0.7 Co 2.3 O 4 A method of preparing an electrocatalyst, comprising the steps of:
step 3, transferring the mixed solution into a 50 mL high-pressure hydrothermal kettle with a polytetrafluoroethylene lining stainless steel, adding pretreated foamy copper, putting the mixture into an oven, setting the temperature to be 120 ℃, setting the time to be 6 to 12 hours, and after the reaction is finished, placing the mixture into the hydrothermal kettle for natural cooling;
step 4, taking the material with the precursor catalyst from the hydrothermal kettle, repeatedly washing the material with deionized water, and then placing the material in a 70 ℃ drying oven for drying for 6 hours; after drying, calcining the material in a muffle furnace for 1 to 2 hours at 200 to 400 ℃ at a heating rate of 2 ℃/min; and obtaining the cobalt-copper spinel catalyst uniformly growing on the substrate after the calcination is finished.
Optionally, the cobalt salt is cobalt chloride hexahydrate or cobalt nitrate hexahydrate, and the copper salt is copper chloride hexahydrate or copper nitrate trihydrate; wherein, the content of cobalt element is 1 mmol, and the content of copper element is 0.5 mmol.
Further, the molar ratio of the cobalt nitrate hexahydrate, the copper nitrate trihydrate, the ammonium fluoride and the urea is 1;
and after the cobalt salt is dissolved in deionized water, the concentration range is 0.025 to 0.035 mol/L.
The invention also requests to protect the cobalt-based spinel Cu prepared by the method 0.7 Co 2.3 O 4 Electrocatalyst of said Cu 0.7 Co 2.3 O 4 The electrocatalyst has a sea urchin-shaped structure, the size is 7-13 mu m, and the sea urchin thorn diameter is less than 100nm.
The prepared catalyst is of a spinel structure, and the structural general formula is AB 2 O 4 In which O is 2- With cubic closest packing, the cation A (divalent) occupiesAccording to 1/8 of the tetrahedral voids, cation B (trivalent) occupies 1/2 of the octahedral voids. During the preparation of the material, cu is obtained due to the loss of copper element 0.7 Co 2.3 O 4 Is understood to mean the stoichiometric ratio of (A) to (B), co 2+ /Co 3+ In a quantitative ratio of 0.3 2+ And Co 2+ Filling into the gaps of spinel tetrahedron, and remaining Co 3+ Enter into octahedral voids to form mixed spinel.
In addition, the invention also requests to protect the cobalt-based spinel Cu prepared by the method 0.7 Co 2.3 O 4 Application of an electrocatalyst in electrocatalytic oxidation of glycerol.
Specifically, the prepared self-supported catalyst is used as a working electrode, graphite is used as a counter electrode, hg/HgO is used as a reference electrode, and the self-supported catalyst is assembled into a three-electrode system for producing formate by glycerol oxidation.
Optionally, the electrolyte selected in the electrocatalytic oxidation process of the glycerol is a mixed solution of glycerol and potassium hydroxide; wherein the concentration of the glycerol is 0.3 mol/L, and the concentration of the potassium hydroxide is 1 mol/L.
Further, glycerol in the mixed solution was replaced with methanol at a concentration of 0.3 mol/L.
According to the technical scheme, compared with the prior art, the cobalt-based spinel Cu provided by the invention 0.7 Co 2.3 O 4 The electrocatalyst, the preparation method and the application thereof have the following excellent effects:
compared with the prior art, the preparation scheme provided by the invention can be used for preparing the catalyst with uniform sea urchin-shaped appearance, and the synthesis method is simple and suitable for large-scale production. At the same time, the catalyst exhibits excellent catalytic activity for glycerol. In the oxidation process of the glycerol, the catalyst can reach 10 mA cm only by 1.17V (vs. RHE) voltage -2 When the initial current density of (2) reaches 400mA cm -2 The required voltage is only 1.37V (vs. RHE) at industrial current densities of (2).
In addition, the catalyst has excellent stability, and the catalytic performance of the catalyst is not obviously reduced after the catalyst is continuously operated for 60 hours at the potential of 1.4V (vs. RHE). This is due to the introduction of copper ions and bulk phase migration, which promotes the improvement of intrinsic activity and stability of the catalyst. As shown in fig. 1, the X-ray diffraction pattern analysis demonstrates the successful incorporation of copper. Fig. 2 is a high-resolution X-ray photoelectron spectrum of Cu2p at different calcination times, and it can be confirmed by analyzing the peak area that migration of copper ions occurs inside the crystal. Studies have shown that hexacoordinated copper ions produce zingiber distortion, resulting in increased structural asymmetry, thereby reducing catalyst stability.
More importantly, the reaction voltage required for the oxidation of glycerol is significantly reduced (as shown in fig. 3) compared to the anodic Oxygen Evolution Reaction (OER) in the electrolytic water reaction, with much broader development space.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is Cu prepared in example 1 0.7 Co 2.3 O 4 X-ray diffraction analysis (XRD) pattern of the catalyst material.
FIG. 2 is Cu prepared in example 1 0.7 Co 2.3 O 4 Cu2p high resolution X-ray photoelectron spectroscopy (XPS) plot of the catalyst material.
FIG. 3 is Cu prepared in example 1 0.7 Co 2.3 O 4 Scanning Electron Microscope (SEM) images of the catalyst material.
FIG. 4 is Cu prepared in example 1 0.7 Co 2.3 O 4 Polarization curve (LSV) plot of catalyst material in glycerol and potassium hydroxide mixed electrolyte.
FIG. 5 is Cu prepared in example 1 0.7 Co 2.3 O 4 Constant current of catalyst material in methanol and potassium hydroxide mixed electrolyteAnd (6) testing a curve.
FIG. 6 is Cu prepared in examples 1 and 3 0.7 Co 2.3 O 4 Polarization curves (LSV) of the catalyst materials in glycerol and potassium hydroxide mixed electrolytes are compared.
FIG. 7 is Cu prepared in example 1 0.7 Co 2.3 O 4 Polarization curve (LSV) plot of catalyst material in mixed electrolyte of methanol and potassium hydroxide.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings of the specification, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention will be further specifically illustrated by the following examples for better understanding, but the present invention is not to be construed as being limited thereto, and certain insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing disclosure are intended to be included within the scope of the invention.
The technical solution of the present invention will be further described with reference to the following specific examples.
Example 1
Self-supporting Cu 0.7 Co 2.3 O 4 The preparation method of the catalyst comprises the following specific steps:
And transferring the mixed solution into a 50 mL high-pressure hydrothermal kettle with a polytetrafluoroethylene lining stainless steel, adding pretreated foamy copper, and putting the mixture into an oven at the set temperature of 120 ℃ for 12 hours. And naturally cooling the hydrothermal kettle after the reaction is finished.
Step 3, taking out the material with the precursor catalyst from the hydrothermal kettle, repeatedly washing the material with deionized water, and then placing the material in a 70 ℃ drying oven for drying for 6 hours; after drying, calcining the material in a muffle furnace for 1 h at 300 ℃ at a heating rate of 2 ℃/min; after the calcination, the cobalt-copper spinel catalyst uniformly grown on the substrate was obtained, and the X-ray diffraction pattern of the catalyst was as shown in fig. 1. The scanning electron micrograph is shown in FIG. 3.
Example 2
And (3) performing an electrochemical performance test by using a conventional three-electrode system electrolytic cell, and performing the electrochemical performance test by using a Shanghai Chenghua CHI 760E workstation to verify the catalytic activity of the catalyst.
Graphite as a counter electrode, hg/HgO (1 mol/L KOH) as a reference electrode, cu was supported 0.7 Co 2.3 O 4 Cutting the foamed copper of the catalyst into 1 × 1 cm -2 The size of the electrolyte is used as a working electrode, and the electrolyte is a mixed solution containing 0.3 mol/L of glycerol and 1mol/L of KOH. Specifically, argon is used as a circulating gas, 30 min of argon is firstly introduced to remove impurity gases in the electrolyte before an electrochemical test is started, CV activation is carried out under the voltage range of 0 to 0.5V (vs. Hg/HgO), the sweep rate is 10 mV/s, the number of scanning turns is 20, and the activation of the catalyst is completed.
Then, a polarization curve test is carried out, the voltage range is set to be 0 to 0.6V, the sweeping speed is 10 mV/s, the iR compensation is 85 percent, the result of the polarization curve is shown in figure 4, and the prepared Cu 0.7 Co 2.3 O 4 The catalyst shows excellent catalytic performance for glycerol oxidation. Reach 10 mA cm -2 、100 mA·cm -2 And 400mA · cm -2 The voltage required for the current density was 1.17V each RHE 、1.27 V RHE And 1.37V RHE The reduction was over 240 mV compared to the OER reaction.
In addition, the Tafel slope and impedance indicate the catalyst Cu 0.7 Co 2.3 O 4 Has faster reaction kinetics and electron transfer speed. On one hand, the performance of the catalyst is improved because the sea urchin-shaped appearance increases the exposure of active sites and the contact area with electrolyte, and meanwhile, the self-supporting material avoids the use of a binder, so that the charge transfer resistance is reduced; on the other hand, the introduction of copper atoms changes the electron local environment, thereby improving the intrinsic activity of the catalyst.
The stability test using the constant current curve showed that the catalyst showed excellent durability at a voltage of 1.4V (vs. RHE), the catalytic activity had little decay after 60h, and the stability test results are shown in fig. 5.
Example 3
Self-supporting Cu 0.7 Co 2.3 O 4 The preparation method of the catalyst comprises the following specific steps:
And transferring the mixed solution into a 50 mL high-pressure hydrothermal kettle with a polytetrafluoroethylene lining stainless steel, adding pretreated foamy copper, and putting the mixture into an oven at the set temperature of 120 ℃ for 12 hours. And naturally cooling the hydrothermal kettle after the reaction is finished.
3, taking out the material with the precursor catalyst from the hydrothermal kettle, repeatedly washing the material with deionized water, and then placing the material in a 70 ℃ oven for drying for 6 hours; after drying, calcining the material in a muffle furnace for 2h at 300 ℃ at a heating rate of 2 ℃/min; and obtaining the cobalt-copper spinel catalyst uniformly growing on the substrate after the calcination is finished.
Compared with example 1, example 3 has longer calcination time, when the calcination time is prolonged, according to the Cu2p high resolution X-ray photoelectron spectrum shown in FIG. 2, more copper atoms located in the tetrahedral space migrate into the octahedral space to form six coordination, and according to the research, the six coordination copper atoms are easy to generate ginger Taylor distortion, thereby causing the stability of the crystal structure to be reduced and the intrinsic activity of the catalyst to be attenuated. In FIG. 2, cu Oh 2+ Represents copper atoms in octahedral gaps, cu Td 2+ Representing the copper atoms located in the tetrahedral interstitials. Cu (copper) 0.7 Co 2.3 O 4 -1 represents a calcination time of 1 h 0.7 Co 2.3 O 4 -2 represents a calcination time of 2 h.
In addition, when the calcination time is 2 hours, the sea urchin-like morphology of the catalyst partially collapses, resulting in a decrease in exposed catalytically active sites, further reducing the catalytic activity of the catalyst.
Example 4
The electrochemical performance test was performed using a conventional three-electrode electrolytic cell, and the catalytic activity of the catalyst was verified by performing the electrochemical performance test using the Shanghai Chenghua CHI 760E workstation.
Graphite as a counter electrode and Hg/HgO (1 mol/L KOH) as a reference electrode, the copper foam supporting the catalyst prepared in example 3 was cut into 1X 1 cm pieces -2 The size of the electrolyte is used as a working electrode, and the electrolyte is a mixed solution containing 0.3 mol/L of glycerol and 1mol/L of KOH. Specifically, argon is used as a circulating gas, 30 min of argon is firstly introduced to remove impurity gases in the electrolyte before the electrochemical test is started, CV activation is carried out under the voltage range of 0 to 0.5V (vs. Hg/HgO), the sweep rate is 10 mV/s, the number of scanning turns is 20, and the catalytic pair is completedActivation of the agent.
Then, a polarization curve test was carried out, the voltage range was set to 0 to 0.6V, the sweep rate was 10 mV/s, and the iR offset was 85%, and the results of the polarization curve are shown in FIG. 6, in which the catalytic activity of example 3 was reduced as compared with example 1. This is due to the collapse of the catalyst morphology reducing the exposure of active sites and the excessive migration of copper atoms inside the crystal reducing the stability of the catalyst.
Example 5
The electrochemical performance test was performed using a conventional three-electrode electrolytic cell, and the catalytic activity of the catalyst was verified by performing the electrochemical performance test using the Shanghai Chenghua CHI 760E workstation.
Graphite as a counter electrode, hg/HgO (1 mol/L KOH) as a reference electrode, cu was supported 0.7 Co 2.3 O 4 Cutting the foamed copper of the catalyst into 1 × 1 cm -2 The size of the electrolyte is used as a working electrode, and the electrolyte is a mixed solution containing 0.3 mol/L methanol and 1mol/L KOH. Specifically, argon is used as a circulating gas, 30 min of argon is firstly introduced to remove impurity gases in the electrolyte before an electrochemical test is started, CV activation is carried out under the voltage range of 0 to 0.5V (vs. Hg/HgO), the sweep rate is 10 mV/s, the number of scanning turns is 20, and the activation of the catalyst is completed.
Then, a polarization curve test is carried out, the voltage range is set to be 0 to 0.6V, the sweeping speed is 10 mV/s, the iR compensation is 85 percent, the result of the polarization curve is shown in figure 2, and the prepared Cu 0.7 Co 2.3 O 4 The catalyst shows excellent catalytic performance for glycerol oxidation. Up to 10 mA cm -2 、100 mA·cm -2 And 400mA · cm -2 The voltage required for the current density was 1.17V each RHE 、1.27 V RHE And 1.37V RHE The reduction was over 240 mV compared to the OER reaction.
In addition, the Tafel slope and impedance indicate the catalyst Cu 0.7 Co 2.3 O 4 Has faster reaction kinetics and electron transfer speed. The improvement of the catalyst performance is caused by the sea urchin-shaped appearance, the exposure of active sites and the contact area of the active sites and electrolyte are increased, and meanwhile, the self-supporting materialThe material avoids the use of a binder, thereby reducing the charge transfer resistance; on the other hand, the electron local environment is changed due to the synergistic effect between the bimetallic catalysts, so that the intrinsic activity of the catalysts is improved.
Example 5 Glycerol in the electrolyte was replaced with methanol, and the electrochemical performance was also excellent up to 400mA cm after polarization curve testing using an electrochemical workstation -2 The voltage required for the current density was 1.51V (vs. RHE), and the results are shown in FIG. 7.
The overpotential required for the electro-oxidation of methanol is relatively large compared to the electro-oxidation of glycerol, on the one hand because glycerol is a three-molecule hydroxyl alcohol, with the same concentration of glycerol and methanol, glycerol having a richer number of hydroxyl groups, and on the other hand because methanol is a primary alcohol, while glycerol contains primary and secondary alcohols, with the secondary alcohol reacting more readily with the catalyst.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. Cobalt-based spinel Cu 0.7 Co 2.3 O 4 A method for preparing an electrocatalyst, comprising the steps of:
1) Placing a commercial foamy copper substrate in a hydrochloric acid solution with the concentration of 1 to 3mol/L for 30 to 60 min, and then sequentially washing foamy copper for three times by using ethanol and water for removing an oxide layer on the surface of the foamy copper and residual organic impurities for later use;
2) Weighing cobalt salt, copper salt, ammonium fluoride and urea, dissolving the cobalt salt, the copper salt, the ammonium fluoride and the urea in deionized water, and magnetically stirring for 15 to 30 min to form a uniform light pink mixed solution;
3) Transferring the mixed solution obtained in the step 2) into a polytetrafluoroethylene-lined stainless steel high-pressure hydrothermal kettle, adding the foamy copper pretreated in the step 1), putting the foamy copper into an oven, setting the temperature at 120 ℃ for 6 to 12 hours, and naturally cooling the hydrothermal kettle after the reaction is finished;
4) Taking the material with the precursor catalyst growing out of the hydrothermal kettle, repeatedly washing the material with deionized water, and then placing the material in a 70 ℃ drying oven for drying for 6 hours; after drying, calcining the material in a muffle furnace for 1 to 2 hours at 200 to 400 ℃ at a heating rate of 2 ℃/min; after calcining and sintering, the cobalt-copper spinel catalyst which grows uniformly on the substrate is obtained.
2. Cobalt-based spinel Cu according to claim 1 0.7 Co 2.3 O 4 The preparation method of the electrocatalyst is characterized in that the cobalt salt is cobalt chloride hexahydrate or cobalt nitrate hexahydrate, and the copper salt is copper chloride hexahydrate or copper nitrate trihydrate; wherein, the content of cobalt element is 1 mmol, and the content of copper element is 0.5 mmol.
3. Cobalt-based spinel Cu according to claim 2 0.7 Co 2.3 O 4 The preparation method of the electrocatalyst is characterized in that the molar ratio of the cobalt nitrate hexahydrate, the copper nitrate trihydrate, the ammonium fluoride and the urea is 1;
and after the cobalt salt is dissolved in the deionized water, the concentration range is 0.025 to 0.035 mol/L.
4. Cobalt-based spinel Cu prepared by the method of claim 1 0.7 Co 2.3 O 4 Electrocatalyst, characterized in that the Cu is 0.7 Co 2.3 O 4 The electrocatalyst has a sea urchin-shaped structure, the size of the electrocatalyst is 7 to 13 mu m, and the diameter of a sea urchin thorn is less than 100nm.
5. A as inCobalt-based spinel Cu prepared by the method of claim 1 0.7 Co 2.3 O 4 Electrocatalyst or cobalt-based spinel Cu as claimed in claim 4 0.7 Co 2.3 O 4 The application of the electrocatalyst in the electrocatalytic oxidation of glycerol.
6. The use according to claim 5, characterized in that the prepared self-supported catalyst is used as a working electrode, graphite as a counter electrode and Hg/HgO as a reference electrode, assembled as a three-electrode system for the oxidation of glycerol to formate.
7. The application of the method as claimed in claim 5 or 6, wherein the electrolyte selected in the electrocatalytic oxidation process of the glycerol is a mixed solution of glycerol and potassium hydroxide; wherein the concentration of the glycerol is 0.3 mol/L, and the concentration of the potassium hydroxide is 1 mol/L.
8. The use according to claim 7, wherein the glycerol in the mixed solution is replaced by methanol at a concentration of 0.3 mol/L.
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