CN117418262A - Multilayer-structure titanium-based electrocatalytic electrode for electrochemical oxidation of 5-hydroxymethylfurfural and preparation method thereof - Google Patents
Multilayer-structure titanium-based electrocatalytic electrode for electrochemical oxidation of 5-hydroxymethylfurfural and preparation method thereof Download PDFInfo
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- 239000010936 titanium Substances 0.000 title claims abstract description 69
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 45
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 35
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006056 electrooxidation reaction Methods 0.000 title claims abstract description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000004913 activation Effects 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000001680 brushing effect Effects 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 150000003624 transition metals Chemical class 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000009835 boiling Methods 0.000 claims abstract description 6
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 239000012046 mixed solvent Substances 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 38
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000002484 cyclic voltammetry Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- 238000010411 cooking Methods 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 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 8
- 239000002028 Biomass Substances 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- XXLJGBGJDROPKW-UHFFFAOYSA-N antimony;oxotin Chemical compound [Sb].[Sn]=O XXLJGBGJDROPKW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract 3
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract 2
- 239000011229 interlayer Substances 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 8
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- 239000011159 matrix material Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- -1 polyethylene terephthalate Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000010408 sweeping Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000004832 voltammetry Methods 0.000 description 3
- 238000001075 voltammogram Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- DYHPIVADFQHIQZ-UHFFFAOYSA-N [Ni].[Sb].[Sn] Chemical compound [Ni].[Sb].[Sn] DYHPIVADFQHIQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 230000002255 enzymatic effect Effects 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/05—Heterocyclic compounds
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
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Abstract
The invention discloses a multilayer-structure titanium-based electrocatalytic electrode for electrochemical oxidation of 5-hydroxymethylfurfural and a preparation method thereof, wherein the multilayer-structure titanium-based electrocatalytic electrode comprises the following components: a titanium substrate, a tin antimony oxide interlayer, and a combination of single or multiple transition metal oxides as a catalytic layer. Firstly, carrying out pretreatment of alkali liquor washing and acid boiling on titanium sheets; at the same time SnCl 4 And SbCl 3 Dissolving in n-butanol, adding appropriate amount of concentrated hydrochloric acid to inhibit hydrolysis, and mixing to obtain solutionA, A is as follows; then brushing the titanium surface, putting the titanium surface into an oven and a muffle furnace for drying, repeating the steps for a plurality of times, and performing electrochemical activation to obtain an intermediate layer titanium electrode; and (3) dissolving the salt of the transition metal in a mixed solvent of water, ethanol and n-butanol according to a certain proportion, fully mixing to obtain a solution B, brushing the solution B on the surface of the intermediate layer titanium electrode, and repeating the brushing for a plurality of times to obtain the transition metal oxide electrocatalytic electrode with a multilayer structure. The electrocatalytic electrode prepared by the invention shows high stability when the biomass-based platform compound 5-hydroxymethylfurfural is converted into 2, 5-furandicarboxylic acid by electrochemical conversion.
Description
Technical Field
The invention belongs to the technical field of organic electronic synthesis, and particularly relates to a preparation method of a titanium-based electrocatalytic electrode with a multilayer structure for electric oxidation synthesis.
Background
5-Hydroxymethylfurfural (HMF) is a biomass-based platform compound derived from glucose, fructose or cellulose, the use of which allows performance compensation and partial replacement of petroleum-based chemicals. Because the HMF has a multifunctional structure, the HMF can be converted into other products with high added value, and is widely applied to the fields of pharmacy, fine chemical industry, fuel and the like. Among them, the oxidation product 2, 5-furandicarboxylic acid (FDCA) thereof is of interest. FDCA can be used as a monomer to replace petroleum-based terephthalic acid (TPA) (a monomer to produce polyethylene terephthalate (PET)) to produce biomass-based plastics, wherein polyethylene 2, 5-furandicarboxylate (PEF) and polypropylene 2, 5-furandicarboxylate (PPF) have superior thermodynamic properties in gas barrier, water barrier and ease of processing than PET. In addition, the modified chitosan can also be used as a bactericide and a chelating agent, and has development potential and application value. The preparation of FDCA by selective oxidation of HMF can be achieved using chemical catalysis, enzymatic catalysis, but these methods may be limited by environmental pollution, severe reaction conditions, or low reaction efficiency. Therefore, the electrochemical method for preparing FDCA becomes a hot spot of current research, and the electrochemical method is mild in condition, avoids using a strong oxidant and can utilize green electricity. In addition, the reaction has strong starting and stopping operability, and is a clean, efficient and convenient way.
In recent years, researchers have developed a number of highly efficient electrocatalysts for the electrooxidation of HMF, and the challenge currently faced is to achieve stable operation of the electrode under industrial electrolysis conditions. The electrocatalytic electrode consists of a catalyst and a matrix, and a commonly used carbon matrix is easily oxidized under the strong oxidation condition in an aqueous solution to cause structural collapse and falling of the surface catalyst. The shape stability electrode matrix is an effective way to improve the stability of the electrode, and patent CN 115613070A discloses a titanium-based tin-antimony-nickel metal coating electrode which is applied to preparing ozone by electrolyzing water and has high oxygen evolution overpotential, but the problem that the conductivity of the electrode is reduced and then the electrode is invalid due to passivation of the Ti matrix is ignored.
Disclosure of Invention
The invention aims to develop an electrocatalytic electrode of high-added-value fine chemicals for preparing 2, 5-furandicarboxylic acid by electrocatalytic oxidation of 5-hydroxymethylfurfural, replace an unstable nickel-based electrode used under the system, provide a titanium-based electrocatalytic electrode with a multilayer structure and a preparation method thereof, and be applied to preparing 2, 5-furandicarboxylic acid by high-efficiency electrocatalytic conversion of 5-hydroxymethylfurfural. The tin antimony oxide intermediate layer after surface activation prevents Ti from contacting the catalytic layer or electrolyte to be passivated, and improves the conductivity of the titanium electrode serving as an anode. In addition, the electrochemical activation also increases the roughness of the intermediate layer, and provides a larger contact area for the catalytic layer to be supported. The whole electrode structure is stable and the durability is strong.
For this purpose, the invention adopts the following technical scheme:
the preparation method of the titanium-based electrocatalytic electrode with the multilayer structure for electrochemical oxidation of 5-hydroxymethylfurfural comprises the following steps:
(1) Pretreatment of titanium sheets:
the Ti sheet is subjected to alkali liquor washing and acid cooking treatment, and the specific method comprises the following steps: the Ti sheet was subjected to ultrasonic treatment in 10wt% NaOH for 5 minutes to remove surface oil stains, then was subjected to boiling treatment in 30% hydrochloric acid solution for 30 minutes to remove surface oxide films, and finally was washed with deionized water and stored.
(2) Preparation of an intermediate layer:
SnCl is added 4 And SbCl 3 Dissolving in n-butanol, adding concentrated hydrochloric acid to prevent hydrolysis, brushing the mixture A on pretreated Ti substrate with brush, drying in oven, and thermal decomposing in muffle furnace. Repeatedly brushing and thermally decomposing for several times, 5 minutes each time, and thermally decomposing for one hour at 500 ℃ for the last time; snCl 4 And SbCl 3 The molar ratio is 9:1;
(3) Electrochemical activation of the intermediate layer:
washing the prepared intermediate layer titanium electrode with deionized water (> 18.25M omega), and then placing the intermediate layer titanium electrode in 0.05-1 mol/L potassium hydroxide aqueous solution for electrochemical activation; the electrochemical activation method comprises the following steps: placing the electrode in 0.1mol/L potassium hydroxide solution, and carrying out cyclic voltammetry scanning for 10-20 times between-1.5V and 2V vs. Hg/HgO;
(4) Preparation of the catalytic layer:
and (3) dissolving the salt solution of the transition metal in a mixed solvent of water, ethanol and n-butanol, and uniformly mixing to obtain a solution B. And uniformly brushing the mixed solution B in an intermediate layer surface oven after electrochemical activation by using a brush, drying at 120 ℃ for 5 minutes, and then placing in a muffle furnace for thermal decomposition at 500 ℃ for 5 minutes. Repeatedly brushing and thermally decomposing for 10 times, and finally placing the titanium-based oxide electrode in a muffle furnace at 500 ℃ for thermal decomposition for 1 hour to obtain the titanium-based oxide electrode with the multilayer structure; the salt of transition metal is NiCl 2 、CuCl 2 、ZnCl 2 、FeCl 3 、CoCl 2 One or more of the following.
Further, the muffle furnace temperature in the step (2) is set to 500 ℃.
Further, the brush coating thermal decomposition was repeated 15 times in the step (2).
Further, in the step (4), the volume ratio of water to ethanol to n-butanol is 2:1:1;
further, the total concentration of the salt solution of the transition metal in the solution B in the step (4) is 1-2 mol/L.
The invention has the beneficial effects that:
(1) The intermediate titanium electrode is used for replacing the nickel-based electrocatalytic electrode, so that the phenomenon that the electrode gradually fails due to matrix expansion is avoided in the alkaline electrolyte, and the stability of the electrocatalytic reaction is improved;
(2) The electrochemical activation intermediate layer inhibits passivation of the titanium matrix, and enhances the binding force between the intermediate layer and the catalytic layer, so that the overall stability of the electrode is improved;
(3) The catalytic layer prepared by using the thermal decomposition method contains rich oxygen vacancies, so that the electrocatalytic performance of the electrode is enhanced;
(4) The transition metal hydroxide is used as an electrocatalyst active substance, so that the cost is low, and the consumption of noble metals is avoided.
Drawings
FIG. 1 is an SEM image of an electrocatalytic electrode prepared according to example 1;
FIG. 2 is a linear voltammogram of an electrocatalytic electrode of example 2;
FIG. 3 is a graph showing the concentration change of the electrolytic reactant and product of the electrocatalytic electrode of example 3;
FIG. 4 is an SEM image of an electrocatalytic electrode of example 4;
FIG. 5 is a linear voltammogram of an electrocatalytic electrode of example 5;
FIG. 6 is an XRD pattern for the electrocatalytic electrode of example 6;
FIG. 7 is a linear voltammogram of an electrocatalytic electrode of example 7.
Detailed Description
The invention is further illustrated by the following examples:
example 1:
the preparation method of the titanium-based electrocatalytic electrode with the multilayer structure comprises the following steps:
(1) Pretreatment of titanium sheets:
a Ti sheet of 1cm by 2cm by 0.08cm was subjected to ultrasonic treatment in 10% by weight NaOH for 5 minutes to remove surface oil stains, and then subjected to boiling treatment in a 30% by volume hydrochloric acid solution for 30 minutes to remove surface oxide films. And finally, washing with deionized water.
(2) Preparation of an intermediate layer:
0.99mol/L SnCl 4 And 0.11mol/L SbCl 3 Dissolving in n-butanol, adding 100 μl of concentrated hydrochloric acid to prevent hydrolysis, and preparing mixed solution A. The mixed solution A is evenly brushed on the Ti substrate after pretreatment by a brush, is put into an oven for drying for 5 minutes at 120 ℃, and is then put into a muffle furnace at 500 ℃ for thermal decomposition for 5 minutes. The brush coating is repeated for thermal decomposition 15 times, and the final thermal decomposition is carried out at 500 ℃ for one hour.
(3) Electrochemical activation of the intermediate layer:
SnSbO prepared by the method x The Ti electrode is put into 0.1mol/L KOH solutionThe line cyclic voltammetry scans for 10 circles, the potential is set to be-1.5V-2V vs. Hg/HgO, and the scanning speed is 50mV/s.
(4) Preparation of the catalytic layer:
NiCl with the concentration of 0.77mol/L respectively 2 And 0.33mol/L CuCl 2 Dissolving in a solvent with a volume ratio of 2:1:1, water, ethanol and n-butanol, and uniformly mixing to obtain a solution B. And (3) brushing the mixed solution B on the surface of the intermediate layer after electrochemical activation uniformly by using a brush, placing the intermediate layer in an oven for drying at 120 ℃ for 5 minutes, and then placing the intermediate layer in a muffle furnace at 500 ℃ for thermal decomposition for 5 minutes. Repeatedly brush-coating and thermally decomposing for 10 times, and thermally decomposing for one hour at 500 ℃ for the last time to obtain NiO-CuO 0.3 /SnSbO x Ti electrode.
Example 2:
NiO-CuO prepared in example 1 0.3 /SnSbO x The Ti electrode electrocatalytic performance test comprises the following specific steps:
the electrocatalytic performance of the electrode on biomass-based compound HMF was tested using linear voltammetry scanning (LSV)
Testing was performed using a prinston V3 electrochemical workstation, in a single chamber cell. Respectively preparing electrolyte A:100mL of 0.1mol/L KOH aqueous solution, electrolyte B: 0.1mol/L KOH aqueous solution containing 10mmol/L HMF. The nickel hydroxide thin film titanium electrode prepared in example 1 was used as a working electrode, a Pt sheet was used as a counter electrode, and Hg/HgO was used as a reference electrode to construct a three-electrode test system. LSV test is carried out on the two electrodes in electrolyte A and electrolyte B respectively, the potential range is 0-1.335V vs. Hg/HgO, and the sweeping speed is 10mV/s. As shown in fig. 3, in the electrolyte B containing HMF, the overpotential of the anodic reaction moves to the low potential direction, and the catalytic current is significantly higher than that of the blank electrolyte a, indicating that the prepared multilayer titanium-based electrocatalytic electrode has excellent electrocatalytic effect on HMF.
Example 3:
the method for preparing FDCA by electrocatalytic oxidation of HMF comprises the following steps:
the reaction was carried out in undivided cells using a prinston V3 electrochemical workstation. The electrolyte is 0.1mol/L KOH aqueous solution containing 10mmol/L HMF, the electrode prepared in the example 2 is used as a working electrode and Hg/HgO reference electrode is inserted into the electrolyte, stirring is set at 350rpm, a Pt sheet electrode is used as a counter electrode and is inserted into a cathode region, a 0.745V vs. Hg/HgO potential is applied for constant potential electrolysis test, and FIG. 4 is a variation curve of yield in different periods, wherein the prepared multilayer-structure titanium-based electrocatalytic electrode has good electrolysis performance on HMF.
Example 4:
the preparation method of the titanium-based electrocatalytic electrode with the multilayer structure comprises the following steps:
a Ti sheet of 1cm by 2cm by 0.08cm was subjected to ultrasonic treatment in 10% by weight NaOH for 5 minutes to remove surface oil stains, and then subjected to boiling treatment in a 30% by volume hydrochloric acid solution for 30 minutes to remove surface oxide films. And finally, washing with deionized water. 0.99mol/L SnCl 4 And 0.11mol/L SbCl 3 Dissolving in n-butanol, adding 100 μl of concentrated hydrochloric acid to prevent hydrolysis, and preparing mixed solution A. The mixed solution A is evenly brushed on the Ti substrate after pretreatment by a brush, is put into an oven for drying for 5 minutes at 120 ℃, and is then put into a muffle furnace at 500 ℃ for thermal decomposition for 5 minutes. The brush coating is repeated for thermal decomposition 15 times, and the final thermal decomposition is carried out at 500 ℃ for one hour.
SnSbO prepared by the method x The Ti electrode is placed in 0.1mol/L KOH solution for 10 circles of cyclic voltammetry scanning, the potential is set to be-1.5V-2V vs. Hg/HgO, and the scanning speed is 50mV/s.
NiCl with the concentration of 0.99mol/L respectively 2 And 0.11mol/L ZnCl 2 The volume ratio of the solution is 2:1:1, ethanol and n-butanol, and uniformly mixing to obtain a solution B. And (3) brushing the mixed solution B on the surface of the intermediate layer after electrochemical activation uniformly by using a brush, placing the intermediate layer in an oven for drying at 120 ℃ for 5 minutes, and then placing the intermediate layer in a muffle furnace at 500 ℃ for thermal decomposition for 5 minutes. Repeatedly brush-coating and thermally decomposing for 10 times, and thermally decomposing for one hour at 500 ℃ for the last time to obtain NiO-ZnO 0.1 /SnSbO x Ti electrode.
Example 5:
for NiO-ZnO prepared in example 4 0.1 /SnSbO x The Ti electrode electrocatalytic performance test comprises the following specific steps:
the electrocatalytic performance of the electrode on biomass-based compound HMF was tested using linear voltammetry scanning (LSV)
Testing was performed using a prinston V3 electrochemical workstation, in a single chamber cell. Respectively preparing electrolyte A:100mL of 0.1mol/L KOH aqueous solution, electrolyte B: 0.1mol/L KOH aqueous solution containing 10mmol/L HMF. The nickel hydroxide thin film titanium electrode prepared in example 1 was used as a working electrode, a Pt sheet was used as a counter electrode, and Hg/HgO was used as a reference electrode to construct a three-electrode test system. LSV test is carried out on the two electrodes in electrolyte A and electrolyte B respectively, the potential range is 0-1.335V vs. Hg/HgO, and the sweeping speed is 10mV/s. As shown in fig. 3, in the electrolyte B containing HMF, the overpotential of the anodic reaction moves to the low potential direction, and the catalytic current is significantly higher than that of the blank electrolyte a, indicating that the prepared multilayer titanium-based electrocatalytic electrode has excellent electrocatalytic effect on HMF.
Example 6:
the preparation method of the titanium-based electrocatalytic electrode with the multilayer structure comprises the following steps:
a Ti sheet of 1cm by 2cm by 0.08cm was subjected to ultrasonic treatment in 10% by weight NaOH for 5 minutes to remove surface oil stains, and then subjected to boiling treatment in a 30% by volume hydrochloric acid solution for 30 minutes to remove surface oxide films. And finally, washing with deionized water. 0.99mol/L SnCl 4 And 0.11mol/L SbCl 3 Dissolving in n-butanol, adding 100 μl of concentrated hydrochloric acid to prevent hydrolysis, and preparing mixed solution A. The mixed solution A is evenly brushed on the Ti substrate after pretreatment by a brush, is put into an oven for drying for 5 minutes at 120 ℃, and is then put into a muffle furnace at 500 ℃ for thermal decomposition for 5 minutes. The brush coating is repeated for thermal decomposition 15 times, and the final thermal decomposition is carried out at 500 ℃ for one hour.
SnSbO prepared by the method x The Ti electrode is placed in 0.1mol/L KOH solution for 10 circles of cyclic voltammetry scanning, the potential is set to be-1.5V-2V vs. Hg/HgO, and the scanning speed is 50mV/s.
NiCl with concentration of 1.1mol/L respectively 2 The volume ratio of the solution is 2:1:1, ethanol and n-butanol, and uniformly mixing to obtain a solution B. Brushing the mixed solution B on the surface of the intermediate layer after electrochemical activation uniformly by using a brush, and placing the intermediate layer in an oven for baking at 120 DEG CDried for 5 minutes and then placed in a muffle furnace at 500 ℃ for thermal decomposition for 5 minutes. Repeatedly brush-coating and thermally decomposing for 10 times, and thermally decomposing at 500 ℃ for one hour for the last time to obtain NiO/SnSbO x Ti electrode.
Example 7:
for NiO/SnSbO prepared in example 6 x The Ti electrode electrocatalytic performance test comprises the following specific steps:
the electrocatalytic performance of the electrode on biomass-based compound HMF was tested using linear voltammetry scanning (LSV)
Testing was performed using a prinston V3 electrochemical workstation, in a single chamber cell. Respectively preparing electrolyte A:100mL of 0.1mol/L KOH aqueous solution, electrolyte B: 0.1mol/L KOH aqueous solution containing 10mmol/L HMF. The nickel hydroxide thin film titanium electrode prepared in example 1 was used as a working electrode, a Pt sheet was used as a counter electrode, and Hg/HgO was used as a reference electrode to construct a three-electrode test system. LSV test is carried out on the two electrodes in electrolyte A and electrolyte B respectively, the potential range is 0-1.335V vs. Hg/HgO, and the sweeping speed is 10mV/s. As shown in fig. 3, in the electrolyte B containing HMF, the overpotential of the anodic reaction moves to the low potential direction, and the catalytic current is significantly higher than that of the blank electrolyte a, indicating that the prepared multilayer titanium-based electrocatalytic electrode has excellent electrocatalytic effect on HMF.
Finally, it should be noted that: the above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The preparation method of the titanium-based electrocatalytic electrode with the multilayer structure for electrochemical oxidation of 5-hydroxymethylfurfural is characterized by comprising the following steps of:
(1) Pretreatment of titanium sheets:
washing Ti sheets with alkali liquor and carrying out acid cooking treatment;
(2) Preparation of an intermediate layer:
SnC is to be treatedl 4 And SbCl 3 Dissolving in n-butanol, adding concentrated hydrochloric acid to prevent hydrolysis, brushing the mixed solution A on the pretreated Ti substrate with a brush to obtain a mixed solution A, drying in an oven, and thermally decomposing in a muffle furnace; repeatedly brushing and thermally decomposing for several times, 5 minutes each time, and thermally decomposing for one hour for the last time; snCl 4 And SbCl 3 The molar ratio is 9:1;
(3) Electrochemical activation of the intermediate layer:
washing the prepared intermediate layer titanium electrode with deionized water, and then placing the intermediate layer titanium electrode in 0.05-1 mol/L potassium hydroxide aqueous solution for electrochemical activation; the electrochemical activation method comprises the following steps: placing the electrode in 0.1mol/L potassium hydroxide solution, and carrying out cyclic voltammetry scanning for 10-20 times between-1.5V and 2V vs. Hg/HgO;
(4) Preparation of the catalytic layer:
dissolving a salt solution of transition metal in a mixed solvent of water, ethanol and n-butanol, and uniformly mixing to obtain a solution B; uniformly brushing the mixed solution B in an intermediate layer surface oven after electrochemical activation by using a brush, drying at 120 ℃ for 5 minutes, and then placing in a muffle furnace for thermal decomposition at 500 ℃ for 5 minutes; repeatedly brushing and thermally decomposing for 10 times, and finally placing the titanium-based oxide electrode in a muffle furnace at 500 ℃ for thermal decomposition for 1 hour to obtain the titanium-based oxide electrode with the multilayer structure; the salt of transition metal is NiCl 2 、CuCl 2 、ZnCl 2 、FeCl 3 、CoCl 2 One or more of the following.
2. The method for preparing the titanium-based electrocatalytic electrode with a multilayer structure for electrochemical oxidation of 5-hydroxymethylfurfural according to claim 1, wherein the specific method for performing alkali liquor washing and acid cooking treatment on the Ti sheets in the step (1) is as follows: the Ti sheet was subjected to ultrasonic treatment in 10wt% NaOH for 5 minutes to remove surface oil stains, then was subjected to boiling treatment in 30% hydrochloric acid solution for 30 minutes to remove surface oxide films, and finally was washed with deionized water and stored.
3. The method for preparing a titanium-based electrocatalytic electrode of a multilayer structure for electrochemical oxidation of 5-hydroxymethylfurfural according to claim 1, wherein the muffle temperature in step (2) is set to 500 ℃.
4. The method for preparing a titanium-based electrocatalytic electrode of a multilayer structure for electrochemical oxidation of 5-hydroxymethylfurfural according to claim 1, wherein the brush pyrolysis is repeated 15 times in step (2).
5. The method for preparing the titanium-based electrocatalytic electrode with a multilayer structure for electrochemical oxidation of 5-hydroxymethylfurfural according to claim 1, wherein the volume ratio of water, ethanol and n-butanol in the step (4) is 2:1:1.
6. The method for preparing the titanium-based electrocatalytic electrode with a multilayer structure for electrochemical oxidation of 5-hydroxymethylfurfural according to claim 1, wherein the total concentration of the salt solution of the transition metal in the solution B in the step (4) is 1-2 mol/L.
7. A titanium-based electrocatalytic electrode of a multilayer structure for electrochemical oxidation of 5-hydroxymethylfurfural prepared by a method according to any one of claims 1 to 6.
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