CN118109854A - Co capable of inducing oxygen vacancies by electrochemical reduction method3O4Electrode material, preparation method and application thereof - Google Patents
Co capable of inducing oxygen vacancies by electrochemical reduction method3O4Electrode material, preparation method and application thereof Download PDFInfo
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- 230000009467 reduction Effects 0.000 title claims abstract description 67
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 48
- 239000001301 oxygen Substances 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
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- 238000000034 method Methods 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 30
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
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- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
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- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 7
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- 238000001035 drying Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
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- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
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- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
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- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
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- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 230000006698 induction Effects 0.000 claims 5
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 abstract description 12
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Abstract
The invention discloses a Co 3O4 electrode material for inducing oxygen vacancies by an electrochemical reduction method, a preparation method and application thereof. Dispersing a Co 3O4 material in a solvent to obtain a catalyst solution, dripping the catalyst solution on carbon paper, and standing to obtain a Co 3O4 electrode material; and (3) activating the Co 3O4 electrode material under the overpotential condition, soaking the electrode material in a neutral electrolyte solution, applying a reduction voltage to perform electrochemical reduction treatment, and obtaining the Co 3O4 electrode material with oxygen vacancies induced by an electrochemical reduction method. The electrode material rich in oxygen vacancies is obtained by adopting an electrochemical reduction method, the material cost is low, and the preparation process is simple and feasible. The Co 3O4 electrode material rich in oxygen vacancies has excellent conversion rate and intrinsic activity on electrocatalytic oxidation of 5-hydroxymethylfurfural, the conversion rate of 5-hydroxymethylfurfural is 93.02%, and the Faraday efficiency of an oxidation product 2, 5-furandicarboxylic acid is 82.49%.
Description
Technical Field
The invention belongs to the technical field of electrocatalytic materials, and particularly relates to a Co 3O4 electrode material for inducing oxygen vacancies by an electrochemical reduction method, and a preparation method and application thereof.
Technical Field
Because of the complex composition and diverse sources of biomass, its conversion is quite difficult, and there is still a serious lack of viable biomass direct value-added technology. Traditional chemical conversion processes are carried out by thermocatalytic processes requiring harsh reaction conditions such as high temperature, high pressure or the use of toxic and expensive catalytic materials. In contrast, the electrocatalytic refining technology is considered to be expected to replace the traditional fossil fuel refining process because not only the renewable biomass raw material can be converted into fine chemicals with high added value and transportable fuels, but also the environment-friendly and green chemical requirements-compliant catalytic oxidation and reduction properties thereof are considered to be expected to replace the traditional fossil fuel refining process, so that the technology is highly valued by researchers. Meanwhile, in the electrocatalytic water splitting hydrogen production method, the kinetics of the oxygen precipitation reaction (OER) are slow and the water splitting efficiency is low, and the Biomass Electrocatalytic Oxidation Reaction (BEOR) is considered as a promising oxygen precipitation substitution reaction because of high added value and low overpotential of the product. Among them, 5-Hydroxymethylfurfural (HMF), one of ten large biomass-derived platform molecules for high-value chemical production in the U.S. department of energy, is widely available from biomass raw materials such as cellulose, starch, fructose, sucrose, and the like. Meanwhile, HMF can be converted into 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), 2, 5-Diformylfuran (DFF), 5-formyl-2-furancarboxylic acid (FFCA), 2, 5-furandicarboxylic acid (FDCA) by electrochemical oxidation. Among these products, FDCA can be used as a monomer to synthesize the polymer polyethylene 2, 5-furandicarboxylate (PEF), a renewable bio-based plastic that can be used to replace polyethylene terephthalate (PET). However, the catalysts reported in the prior literature for the electrocatalytic conversion of biomass mostly adopt noble metal materials, such as Au, pt, pd, ag and (Guangqiang Lv,Zonghang Zhang,et al.Atom level revelation of the synergistic effect between Pd and Au atoms in PdAu nanoalloy catalyst for aerobic oxidation of 5-hydroxymethylfurfural.Chemical Engineering Journal,2023,453,139816.),, which have higher cost and do not accord with the modern green chemical synthesis principle.
As described above, the replacement of the Oxygen Evolution Reaction (OER) by the electrocatalytic oxidation reaction (BEOR) of biomass can further increase the economic value, and the development of a low-cost, environmentally friendly and efficient catalyst with BEOR activity is urgent.
Disclosure of Invention
The invention aims to solve the problem of high cost caused by adopting a noble metal material as BEOR electrocatalyst in the prior art, and provides a Co 3O4 electrode material for inducing oxygen vacancies by an electrochemical reduction method, and a preparation method and application thereof.
The primary aim of the invention is to provide a preparation method of a Co 3O4 electrode material which induces oxygen vacancies by an electrochemical reduction method.
Another object of the invention is to provide a Co 3O4 electrode material that induces oxygen vacancies by electrochemical reduction and its use in electrocatalytic oxidation of 5-hydroxymethylfurfural.
The aim of the invention is achieved by the following technical scheme:
A preparation method of a Co 3O4 electrode material for inducing oxygen vacancies by an electrochemical reduction method comprises the following steps:
(1) Dispersing a Co 3O4 material in a solvent to obtain a catalyst solution, dripping the catalyst solution on carbon paper, and standing to obtain a Co 3O4 electrode material;
(2) And (3) activating the Co 3O4 electrode material obtained in the step (1) under the overpotential condition, soaking the electrode material in a neutral electrolyte solution, applying a reduction voltage to perform electrochemical reduction treatment, and obtaining the Co 3O4 electrode material with oxygen vacancies induced by an electrochemical reduction method.
Preferably, in the step (1), the concentration of Co 3O4 material in the catalyst solution is 8-12 mg/mL;
Further preferably, the concentration of Co 3O4 material in the catalyst solution is 10mg/mL.
Preferably, in the step (1), the solvent comprises isopropanol, water and a perfluorosulfonic acid polymer solution, and the volume ratio of the isopropanol, the water and the perfluorosulfonic acid polymer solution is 8-10: 8-10: 2, the concentration of the perfluorinated sulfonic acid polymer solution is 4-6 wt.% perfluorinated sulfonic acid polymer solution;
Further preferably, the volume ratio of the isopropanol, water and perfluorosulfonic acid polymer solution is 9:9:2; the concentration of the perfluorosulfonic acid polymer solution is 5wt.% of the perfluorosulfonic acid polymer solution;
further preferably, the water is ultrapure water.
Preferably, in the step (1), the carbon paper is double-sided hydrophilic carbon paper; the thickness of the carbon paper is 0.2-0.4 mm;
Preferably, in step (1), the Co 3O4 material is a powder, a nanoparticle, or a microparticle.
Preferably, in the step (1), the area ratio of the volume usage of the catalyst solution to the carbon paper is 40 to 60 μl:2cm 2;
Further preferably, the catalyst solution is dropped on both sides of the carbon paper, and half of the volume of each of the front and back sides is dropped on the carbon paper.
Preferably, in step (1), the time of the standing is not less than 1 hour.
Preferably, in the step (2), the potential of the activation treatment is 0-0.6V vs. Hg/HgO, and the time of the activation treatment is 10-30 min;
Further preferably, the potential of the activation treatment is cyclic voltammetry sweep voltage of 0 to 0.6V vs. Hg/HgO.
Further preferably, the time of the activation treatment is 20 minutes.
Preferably, in the step (2), the electrolyte of the activation treatment is a mixed solution of alkali and HMF; the concentration of OH - in the mixed solution of alkali and HMF is 0.8-1.2M, and the concentration of HMF is 40-60 mM; the alkali is at least one of NaOH and KOH.
Preferably, in the step (2), the reduction voltage applied in the electrochemical reduction treatment is-0.8 to-2.0 vvs.Hg/HgO, and the time of the electrochemical reduction treatment is 0.5 to 10min.
Further preferably, the reduction voltage applied in the electrochemical reduction treatment is a constant voltage.
Further preferably, the reduction voltage applied in the electrochemical reduction treatment is-1.8V vs. Hg/HgO, and the time of the electrochemical reduction treatment is 5min.
Preferably, in the step (2), the neutral electrolyte solution is at least one of a sulfate solution, a nitrate solution and a hydrochloride solution; the concentration of the neutral electrolyte solution is 1-6M;
further preferably, the neutral electrolyte solution is at least one of a sodium sulfate solution, a potassium sulfate solution, a sodium nitrate solution, a potassium nitrate solution, a sodium chloride solution, and a potassium chloride solution.
Further preferably, the neutral electrolyte solution is a sodium sulfate solution, and the concentration of the neutral electrolyte solution is 1M.
Preferably, the preparation method of the Co 3O4 material in the step (1) comprises the following steps:
S1, adding Co salt and alkali into water, and mixing and dissolving to obtain a mixed solution;
S2, carrying out hydrothermal reaction on the mixed solution obtained in the step S1, washing, centrifuging and drying to obtain a precursor material;
S3, placing the precursor material obtained in the S2 in an air atmosphere for roasting to obtain the Co 3O4 material.
Further preferably, in step S1, the molar volume ratio of Co element and water in the Co salt is 0.04 to 0.2mol:40mL; the mol volume ratio of OH - and water in the alkali is 0.01-0.05 mol:40mL;
more preferably, the molar volume ratio of Co element and water in the Co salt is 0.2mol:40mL; the molar volume ratio of OH - and water in the base is 0.05mol:40mL;
further preferably, in step S1, the Co salt is cobalt nitrate; more preferably Co (NO 3)2·6H2 O).
Further preferably, in step S1, the base is at least one of NaOH and KOH.
Further preferably, in step S1, the water is deionized water.
Further preferably, in the step S2, the temperature of the hydrothermal reaction is 120-180 ℃, and the time of the hydrothermal reaction is 3-7 hours;
more preferably, the temperature of the hydrothermal reaction is 180 ℃ and the time of the hydrothermal reaction is 5 hours.
Further preferably, in step S3, the baking temperature is 300-700 ℃ and the baking time is 1-5 h.
More preferably, the calcination temperature is 500 ℃ and the calcination time is 3 hours.
The electrochemical reduction method prepared by the preparation method induces the Co 3O4 electrode material of oxygen vacancies.
The application of the Co 3O4 electrode material for inducing oxygen vacancies by the electrochemical reduction method in the electrocatalytic oxidation reaction of 5-hydroxymethylfurfural.
Preferably, the use is the electrocatalytic oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid.
The electrode material prepared by the invention has the advantages of simple preparation flow, low preparation cost, strong universality of the preparation method, strong regulation and control of the preparation process, remarkable improvement of the performance of the prepared material and the like, and the Co 3O4 electrode material for inducing oxygen vacancies by the electrochemical reduction method prepared by the preferential conditions has high conversion rate, high activity and high selectivity in the electrocatalytic oxidation reaction of 5-hydroxymethylfurfural.
Compared with the prior art, the invention has the following technical effects:
(1) The Co 3O4 electrode material for inducing oxygen vacancies by the electrochemical reduction method provided by the invention has lower energy consumption in the production process and accords with the principle of green chemical synthesis.
(2) The Co 3O4 electrode material for inducing oxygen vacancies by the electrochemical reduction method provided by the invention has the advantages of simple preparation method, large-scale production of all used raw materials and wide sources.
(3) The Co 3O4 electrode material for inducing oxygen vacancies by the electrochemical reduction method provided by the invention adopts the electrochemical reduction method to carry out defect regulation on the electrode material, and can easily prepare the electrode material with oxygen vacancies with different concentrations by regulating reduction conditions such as reduction voltage, reduction duration and electrolyte solution used for reduction.
(4) The Co 3O4 electrode material for inducing oxygen vacancies by the electrochemical reduction method provided by the invention has good electrocatalytic oxidation activity of 5-hydroxymethylfurfural, the conversion rate of 5-hydroxymethylfurfural is 93.02%, and the Faraday efficiency of an oxidation product 2, 5-furandicarboxylic acid is 82.49%.
Drawings
FIG. 1 is an SEM characterization of an electrochemical reduction oxygen vacancy-induced Co 3O4 electrode material prepared in example 1;
FIG. 2 is a cyclic voltammogram of the positive scan segment of the electrode materials prepared in example 1 and comparative example 1;
FIG. 3 is a graph showing the comparison of the conversion of 5-hydroxymethylfurfural to electrode materials prepared in example 1 and comparative example 1;
FIG. 4 is a graph showing the comparison of Faraday efficiencies of the 5-hydroxymethylfurfural oxidation product, 2, 5-furandicarboxylic acid, of the electrode materials prepared in example 1 and comparative example 1;
fig. 5 is an EPR characterization graph of the electrode materials prepared in example 1 and comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail with reference to specific examples and comparative examples. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
Except for the special description, the equipment used in the embodiment and the comparative example are conventional experimental equipment, the materials and the reagents used are all obtained in the market without the special description, and the experimental method without the special description is also a conventional experimental method.
Example 1:
A preparation method of a Co 3O4 electrode material for inducing oxygen vacancies by an electrochemical reduction method comprises the following steps:
(1) To 40mL of deionized water, 0.2mol of Co (NO 3)2·6H2 O and 0.05mol of NaOH) was added, and the mixture was thoroughly mixed and dissolved to obtain a mixed solution.
(2) Transferring the obtained mixed solution into a 50mL polytetrafluoroethylene reaction kettle, performing hydrothermal reaction for 5 hours at 180 ℃, washing the precipitate with deionized water for several times after cooling to room temperature, centrifugally collecting the precipitate, and drying the precipitate in a forced air drying oven at 80 ℃ for 12 hours to obtain a precursor.
(3) And placing the obtained precursor in an air atmosphere, and calcining for 3 hours at 500 ℃ to obtain the Co 3O4 material.
(4) The obtained Co 3O4 material was prepared to obtain a catalyst solution, 50. Mu.L of the catalyst solution was dropped on a piece of carbon paper having a diameter of 16.2mm, and 25. Mu.L each was used on both sides. To ensure complete volatilization of the solution on both sides of the electrode, the electrode carrying the catalyst solution was left to stand at ambient temperature for at least 1 hour to give a Co 3O4 electrode. Wherein the catalyst solution had a concentration of 10mg/mL and contained isopropyl alcohol, ultrapure water and 5wt.% perfluorosulfonic acid polymer solution (available from DuPont, model D520) in a volume ratio of 9:9:2, the carbon paper is double-sided hydrophilic carbon paper with the thickness of 0.3mm and is made of carbon fiber paper (model HCP 030).
(5) The Co 3O4 electrode obtained above was subjected to 10 cycles of Cyclic Voltammetry (CV) scan test (activation treatment) in a mixed solution of 1M KOH and 50mM HMF to ensure that the Co 3O4 electrode reached a steady state, the specific test conditions were as follows: the scanning range is 0.0-0.6V (relative to Hg/HgO reference electrode), and the scanning speed is 10mV/s (2 min per turn). Then soaking in 1M sodium sulfate solution, applying a reduction voltage of-1.8V vs. Hg/HgO for electrochemical reduction treatment, wherein the treatment time is 5min, and obtaining the Co 3O4 electrode material rich in oxygen vacancies.
Example 2:
A preparation method of a Co 3O4 electrode material for inducing oxygen vacancies by an electrochemical reduction method comprises the following steps:
(1) To 40mL of deionized water, 0.04mol of Co (NO 3)2·6H2 O and 0.01mol of NaOH) was added, and the mixture was thoroughly mixed and dissolved to obtain a mixed solution.
(2) Transferring the obtained mixed solution into a 50mL polytetrafluoroethylene reaction kettle, performing hydrothermal reaction for 7 hours at 120 ℃, washing the precipitate with deionized water for several times after cooling to room temperature, centrifugally collecting the precipitate, and drying the precipitate in a forced air drying oven at 80 ℃ for 12 hours to obtain a precursor.
(3) And placing the obtained precursor in an air atmosphere, and calcining for 1h at 700 ℃ to obtain the Co 3O4 material.
(4) The obtained Co 3O4 material was prepared to obtain a catalyst solution, 50. Mu.L of the catalyst solution was dropped on a piece of carbon paper having a diameter of 16.2mm, and 25. Mu.L each was used on both sides. To ensure complete volatilization of the solution on both sides of the electrode, the electrode carrying the catalyst solution was left to stand at ambient temperature for at least 1 hour to give a Co 3O4 electrode. Wherein the catalyst solution had a concentration of 10mg/mL and contained isopropyl alcohol, ultrapure water and 5wt.% perfluorosulfonic acid polymer solution (available from DuPont, model D520) in a volume ratio of 9:9:2, the carbon paper is double-sided hydrophilic carbon paper with the thickness of 0.3mm and is made of carbon fiber paper (model HCP 030).
(5) The Co 3O4 electrode obtained above was subjected to 10 cycles of Cyclic Voltammetry (CV) scan test (activation treatment) in a mixed solution of 1M KOH and 50mM HMF to ensure that the Co 3O4 electrode reached a stable state, and specific test conditions were as follows: the scanning range is 0.0-0.6V (relative to Hg/HgO reference electrode), and the scanning speed is 10mV/s (2 min per turn). Then soaking in 6M potassium nitrate solution, applying a reduction voltage of-2.0V vs. Hg/HgO for electrochemical reduction treatment, wherein the treatment time is 0.5min, and obtaining the Co 3O4 electrode material rich in oxygen vacancies.
Example 3:
A preparation method of a Co 3O4 electrode material for inducing oxygen vacancies by an electrochemical reduction method comprises the following steps:
(1) To 40mL of deionized water, 0.1mol of Co (NO 3)2·6H2 O and 0.03mol of NaOH) was added, and the mixture was thoroughly mixed and dissolved to obtain a mixed solution.
(2) Transferring the obtained mixed solution into a 50mL polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction for 3 hours at 150 ℃, washing the precipitate with deionized water for several times after cooling to room temperature, centrifugally collecting the precipitate, and drying the precipitate in a forced air drying oven at 80 ℃ for 12 hours to obtain the precursor.
(3) And placing the obtained precursor in an air atmosphere, and calcining for 5 hours at 300 ℃ to obtain the Co 3O4 material.
(4) The obtained Co 3O4 material was prepared to obtain a catalyst solution, 50. Mu.L of the catalyst solution was dropped on a piece of carbon paper having a diameter of 16.2mm, and 25. Mu.L each was used on both sides. To ensure complete volatilization of the solution on both sides of the electrode, the electrode carrying the catalyst solution was left to stand at ambient temperature for at least 1 hour to give a Co 3O4 electrode. Wherein the catalyst solution had a concentration of 10mg/mL and contained isopropyl alcohol, ultrapure water and 5wt.% perfluorosulfonic acid polymer solution (available from DuPont, model D520) in a volume ratio of 9:9:2, the carbon paper is double-sided hydrophilic carbon paper with the thickness of 0.3mm and is made of carbon fiber paper (model HCP 030).
(5) The Co 3O4 electrode obtained above was subjected to 10 cycles of Cyclic Voltammetry (CV) scan test (activation treatment) in a mixed solution of 1M KOH and 50mM HMF to ensure that the Co 3O4 electrode reached a stable state, and specific test conditions were as follows: the scanning range is 0.0-0.6V (relative to Hg/HgO reference electrode), and the scanning speed is 10mV/s (2 min per turn). Then soaking in 3M sodium chloride solution, applying a reduction voltage of-0.8V vs. Hg/HgO for electrochemical reduction treatment, wherein the treatment time is 10min, and obtaining the Co 3O4 electrode material rich in oxygen vacancies.
Comparative example 1:
A preparation method of a Co 3O4 electrode material comprises the following steps:
(1) To 40mL of deionized water, 0.2mol of Co (NO 3)2·6H2 O and 0.05mol of NaOH) was added, and the mixture was thoroughly mixed and dissolved to obtain a mixed solution.
(2) Transferring the obtained mixed solution into a 50mL polytetrafluoroethylene reaction kettle, performing hydrothermal reaction for 5 hours at 180 ℃, washing the precipitate with deionized water for several times after cooling to room temperature, centrifugally collecting the precipitate, and drying the precipitate in a forced air drying oven at 80 ℃ for 12 hours to obtain a precursor.
(3) And placing the obtained precursor in an air atmosphere, and calcining for 3 hours at 500 ℃ to obtain the Co 3O4 material.
(4) The obtained Co 3O4 material was prepared to obtain a catalyst solution, 50. Mu.L of the catalyst solution was dropped on a piece of carbon paper having a diameter of 16.2mm, and 25. Mu.L each was used on both sides. To ensure complete volatilization of the solution on both sides of the electrode, the electrode carrying the catalyst solution was left to stand at ambient temperature for at least 1 hour to give a Co 3O4 electrode. Wherein the catalyst solution had a concentration of 10mg/mL and contained isopropyl alcohol, ultrapure water and 5wt.% perfluorosulfonic acid polymer solution (available from DuPont, model D520) in a volume ratio of 9:9:2, the carbon paper is double-sided hydrophilic carbon paper with the thickness of 0.3mm and is made of carbon fiber paper (model HCP 030).
The Scanning Electron Microscope (SEM) image of the oxygen vacancy-rich Co 3O4 electrode material obtained in this example 1 is shown in FIG. 1, and the obtained sample has an octahedral structure with a particle size of about 100-500 nm.
The electrode materials obtained in this example 1 and comparative example 1 were tested for electrocatalytic oxidation activity of 5-hydroxymethylfurfural. Test conditions: the standard three-electrode system is adopted as a test system, the obtained electrode material is adopted as a working electrode, saturated Hg/HgO is adopted as a reference electrode, a platinum mesh is adopted as a counter electrode, a 50mM HMF and 1MKOH mixed solution is adopted as an electrolyte solution, and a test instrument is an Shanghai Chenhua 660E electrochemical workstation. The cyclic voltammetry characteristic curve is tested at room temperature of 25 ℃, and as shown in figure 2, the electrochemical performance of the Co 3O4 electrode material which is rich in oxygen vacancies after electrochemical reduction treatment is obviously improved.
The electrode materials obtained in this example 1 and comparative example 1 were subjected to product tests of electrocatalytic oxidation of 5-hydroxymethylfurfural, which resulted in conversion of 93.02% and 25.19% of 5-hydroxymethylfurfural in example 1 and comparative example 1, respectively (fig. 3), and faradaic efficiencies of 2, 5-furandicarboxylic acid, an oxidized product of 5-hydroxymethylfurfural, were 82.49% and 43.20%, respectively (fig. 4).
The electrode materials obtained in the present examples 1 and comparative example 1 were characterized by using an electron paramagnetic resonance spectrometer, and the oxygen vacancy concentration of the electrode materials obtained in the examples 1 and comparative example 1 was semi-quantitatively analyzed, as shown in fig. 5, the oxygen vacancies of the electrode materials of Co 3O4 after electrochemical reduction treatment are more, which indicates that the electrochemical reduction treatment is a good strategy for inducing the electrode materials to generate oxygen vacancies.
The results of combining fig. 2, 3 and 4 show that the Co 3O4 electrode material prepared by the electrochemical reduction method for inducing oxygen vacancies according to the embodiment of the present invention has high conversion rate of 5-hydroxymethylfurfural, high faraday efficiency of oxidation products and more excellent intrinsic activity.
The results of fig. 2, fig. 3, fig. 4 and fig. 5 show that the concentration of oxygen vacancies of the Co 3O4 electrode material induced by the electrochemical reduction method prepared by the embodiment of the invention is significantly improved, so that the electrode material has more excellent reactivity in the 5-hydroxymethyl electrocatalytic oxidation reaction.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the Co 3O4 electrode material for inducing oxygen vacancies by an electrochemical reduction method is characterized by comprising the following steps:
(1) Dispersing a Co 3O4 material in a solvent to obtain a catalyst solution, dripping the catalyst solution on carbon paper, and standing to obtain a Co 3O4 electrode material;
(2) And (3) activating the Co 3O4 electrode material obtained in the step (1) under the overpotential condition, soaking the electrode material in a neutral electrolyte solution, applying a reduction voltage to perform electrochemical reduction treatment, and obtaining the Co 3O4 electrode material with oxygen vacancies induced by an electrochemical reduction method.
2. The method for producing a Co 3O4 electrode material for oxygen vacancy induction by electrochemical reduction according to claim 1, wherein in step (1), the concentration of the Co 3O4 material in the catalyst solution is 8 to 12mg/mL; the solvent comprises isopropanol, water and a perfluorosulfonic acid polymer solution, wherein the volume ratio of the isopropanol to the water to the perfluorosulfonic acid polymer solution is 8-10: 8-10: 2, the concentration of the perfluorinated sulfonic acid polymer solution is 4-6 wt.% perfluorinated sulfonic acid polymer solution; the carbon paper is double-sided hydrophilic carbon paper; the thickness of the carbon paper is 0.2-0.4 mm; the Co 3O4 material is powder, nano particles or micro particles;
In the step (1), the area ratio of the volume usage of the catalyst solution to the carbon paper is 40-60 mu L:2cm 2; the time of the standing is not less than 1 hour.
3. The method for producing a Co 3O4 electrode material for oxygen vacancy induction by electrochemical reduction according to claim 1, wherein in the step (2), the potential of the activation treatment is 0 to 0.6v vs. hg/HgO, and the time of the activation treatment is 10 to 30min;
In the step (2), the electrolyte subjected to the activation treatment is a mixed solution of alkali and HMF; the concentration of OH - in the mixed solution of alkali and HMF is 0.8-1.2M, and the concentration of HMF is 40-60 mM; the alkali is at least one of NaOH and KOH.
4. The method for producing a Co 3O4 electrode material that induces oxygen vacancies by electrochemical reduction according to claim 1, wherein in step (2), the reduction voltage applied in the electrochemical reduction treatment is-0.8 to-2.0 v vs. hg/HgO, and the time of the electrochemical reduction treatment is 0.5 to 10min;
In the step (2), the neutral electrolyte solution is at least one of sulfate solution, nitrate solution and hydrochloride solution; the concentration of the neutral electrolyte solution is 1-6M.
5. The method for preparing a Co 3O4 electrode material for oxygen vacancy induced by electrochemical reduction according to claim 4, wherein the neutral electrolyte solution is at least one of sodium sulfate solution, potassium sulfate solution, sodium nitrate solution, potassium nitrate solution, sodium chloride solution, and potassium chloride solution.
6. The method for preparing a Co 3O4 electrode material for oxygen vacancy induction by electrochemical reduction according to claim 1, wherein the method for preparing a Co 3O4 material in step (1) comprises the steps of:
S1, adding Co salt and alkali into water, and mixing and dissolving to obtain a mixed solution;
S2, carrying out hydrothermal reaction on the mixed solution obtained in the step S1, washing, centrifuging and drying to obtain a precursor material;
S3, placing the precursor material obtained in the S2 in an air atmosphere for roasting to obtain the Co 3O4 material.
7. The method for preparing a Co 3O4 electrode material for oxygen vacancy induction by electrochemical reduction according to claim 6, wherein in step S1, the molar volume ratio of Co element and water in the Co salt is 0.04 to 0.2mol:40mL; the mol volume ratio of OH - and water in the alkali is 0.01-0.05 mol:40mL;
In the step S1, the alkali is at least one of NaOH and KOH; the Co salt is cobalt nitrate.
8. The method for preparing a Co 3O4 electrode material for oxygen vacancy induction by electrochemical reduction according to claim 6, wherein in step S2, the hydrothermal reaction is carried out at 120 to 180 ℃ for 3 to 7 hours;
In the step S3, the roasting temperature is 300-700 ℃, and the roasting time is 1-5 h.
9. A Co 3O4 electrode material that induces oxygen vacancies by electrochemical reduction produced by the production method according to any one of claims 1 to 8.
10. Use of the Co 3O4 electrode material that induces oxygen vacancies by electrochemical reduction according to claim 9 in electrocatalytic oxidation of 5-hydroxymethylfurfural.
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