CN115786964B - Cobalt-based spinel Cu 0.7 Co 2.3 O 4 Electrocatalyst, preparation method and application thereof - Google Patents
Cobalt-based spinel Cu 0.7 Co 2.3 O 4 Electrocatalyst, preparation method and application thereof Download PDFInfo
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- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 20
- 239000011029 spinel Substances 0.000 title claims abstract description 20
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 17
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 12
- 239000010941 cobalt Substances 0.000 title claims abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- 239000010949 copper Substances 0.000 claims abstract description 57
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 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
- 239000006260 foam Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 150000001868 cobalt Chemical class 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 150000001879 copper Chemical class 0.000 claims abstract description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 26
- 239000003792 electrolyte Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group 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 group 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
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000011010 flushing procedure Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 241000257465 Echinoidea Species 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims 1
- 235000011187 glycerol Nutrition 0.000 abstract description 29
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 5
- 230000002238 attenuated effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- TUWPHPPYOOPWGT-UHFFFAOYSA-J copper cobalt(2+) dicarbonate Chemical compound C([O-])([O-])=O.[Co+2].[Cu+2].C([O-])([O-])=O TUWPHPPYOOPWGT-UHFFFAOYSA-J 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 230000010287 polarization Effects 0.000 description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- 230000004913 activation Effects 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
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- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 241000234314 Zingiber Species 0.000 description 1
- 235000006886 Zingiber officinale Nutrition 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- STXKJSYMVDTOSJ-UHFFFAOYSA-M chlorocopper hexahydrate Chemical group [Cu]Cl.O.O.O.O.O.O STXKJSYMVDTOSJ-UHFFFAOYSA-M 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
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- 239000000446 fuel Substances 0.000 description 1
- 235000008397 ginger Nutrition 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 238000002272 high-resolution X-ray photoelectron spectroscopy Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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Abstract
The invention relates to cobalt-based spinel Cu 0.7 Co 2.3 O 4 The electrocatalyst and the preparation method and the application thereof, a pretreated foam copper carrier is placed in a solution containing cobalt salt, copper salt, urea and ammonium fluoride, and then a basic cobalt copper carbonate precursor is grown on a foam copper substrate by a hydrothermal method; calcining after drying to obtain Cu uniformly distributed on foam copper substrate 0.7 Co 2.3 O 4 An electrocatalyst. It shows excellent catalytic activity and stability in the application of electrooxidized glycerin to formate, and can reach up to 400mA cm only by 1.37V (vs. RHE) ‑2 The electrocatalytic performance is not attenuated after the stable circulation for 60 hours, and the Faraday efficiency of formate is as high as more than 80 percent. The catalyst has simple synthesis process, lower cost and excellent catalytic performance, and has good application prospect in the industry of producing formate by glycerol electrooxidation.
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 The preparation method of the electrocatalyst and the application of the catalyst in realizing the efficient electrocatalytic oxidation of glycerol into formic acid.
Background
The electrocatalytic oxidation technology is used for effectively converting small molecular organic matters into high-value fine chemicals, and is one of novel energy treatment technologies for realizing sustainable green development. The technology can be used for selectively converting small molecular organic matters into a plurality of high-added-value chemical products such as methanol, formic acid, ethylene, acetone and the like at normal temperature and normal pressure. Meanwhile, the electrocatalytic 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 matter electrocatalytic conversion technology has great development potential. The glycerol is used as an industrial micromolecular byproduct with severely excessive productivity, the price is low, the raw material sources are rich, and the formic acid is used as an important raw material in industrial production, is a precursor of various chemical products, is also an anode material of a formic acid fuel cell and an excellent hydrogen storage material, and has higher economic value. Therefore, compared with the electrolysis of water to produce hydrogen and oxygen, the method introduces small molecular organic matters into the electrolyte to produce hydrogen in a coupling way, can greatly reduce the consumption of electric energy, and simultaneously produces and obtains fine chemicals with higher added value than oxygen.
The transition metal oxide is a common electrocatalytic oxidation catalyst at the present stage, and has the advantages of high earth abundance, low cost, wide sources and the like compared with the noble metal oxide catalyst. At present, researchers have initially explored glycerol oxidation, but noble metals are mainly used as raw materials, so that the method has higher production cost, and meanwhile, a large improvement space is provided in terms of current density and stability required by the catalyst. Therefore, the construction of a catalyst with low cost, high current density and long-term stability is of great significance. Among the numerous metal oxides, spinel oxides have unique electronic structures and charge distributions, exhibiting more excellent properties for the electrooxidation of glycerol. Meanwhile, in the multi-metal oxide, the synergistic effect among multiple metals is also greatly helpful for improving the catalytic performance.
Based on the method, proper transition metal elements are selected, and the development and design of the catalyst with low cost, high catalytic performance and long-term stability are one of keys for promoting the glycerol electrooxidation to realize industrial application.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention provides a low-cost and simple-operation cobalt-based spinel Cu 0.7 Co 2.3 O 4 The preparation method of the electrocatalyst and the application of the electrocatalyst in the electrocatalytic oxidation of glycerin have Faraday efficiency of more than 80 percent, and can reach industrial-grade current density (400 mA cm) under lower voltage in a three-electrode system -2 ) The required operating voltage is much lower than for OER reactions. Meanwhile, the method has the advantages of simple preparation, simple and convenient operation and high energy utilization rate.
The cobalt-based spinel Cu prepared by the invention 0.7 Co 2.3 O 4 The electrocatalyst has a sea urchin-shaped special shape, is favorable for full contact of the catalyst and electrolyte, and meanwhile, thorns on the sea urchin shape can expose more catalytic active sites, so that the catalytic activity of glycerol oxidation is increased.
More importantly, the introduction of copper ions and migration inside the crystal adjust the electronic structure inside the crystal and optimize the intrinsic catalytic activity of the catalyst.
In order to achieve the above object, the present invention provides the following technical solutions:
cobalt-based spinel Cu 0.7 Co 2.3 O 4 A method of preparing an electrocatalyst comprising the steps of:
step 1, placing a commercial foamy copper substrate in a hydrochloric acid solution with the concentration of 1-3 mol/L for ultrasonic treatment for 30-60 min, and then sequentially flushing the foamy copper with ethanol and water for three times to remove an oxide layer and residual organic impurities on the surface of the foamy copper;
step 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 together, and magnetically stirring the mixture for 15-30 min to form a uniform light pink mixed solution;
step 3, transferring the mixed solution into a 50 mL polytetrafluoroethylene lining stainless steel high-pressure hydrothermal kettle, adding pretreated foam copper, placing the mixture into an oven, setting the temperature to 120 ℃ for 6-12 hours, and placing the hydrothermal kettle for natural cooling after the reaction is finished;
step 4, taking out the material growing 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 6h; after the drying is finished, calcining the material in a muffle furnace for 1-2 hours at the calcining temperature of 200-400 ℃ at the heating rate of 2 ℃/min; and after the calcination is finished, the cobalt copper spinel catalyst which grows uniformly on the substrate is obtained.
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 mole ratio of cobalt nitrate hexahydrate to copper nitrate trihydrate to ammonium fluoride to urea is 1:0.5:3:6, wherein the mole ratio of cobalt salt to copper salt to ammonium fluoride is 1:0.5:3, and the mole ratio of cobalt salt to urea is 1:4-8;
and after the cobalt salt is dissolved in deionized water, the concentration range is 0.025-0.035 mol/L.
The invention also claims cobalt-based spinel Cu prepared by the method 0.7 Co 2.3 O 4 Electrocatalyst of 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 diameter of sea urchin thorns is smaller than 100nm.
Because the prepared catalyst is of a spinel structure, the general structural formula of the catalyst is AB 2 O 4 Wherein O is 2- Cubic closest packing is done, cation A (divalent) occupies 1/8 of the tetrahedral void, and cation B (trivalent) occupies 1/2 of the octahedral void. In the material preparation process, cu is obtained due to copper element loss 0.7 Co 2.3 O 4 Is understood to be Co 2+ /Co 3+ The number ratio of (C) is 0.3:2, all Cu 2+ And Co 2+ Filling into spinel tetrahedral voids, the remainder Co 3+ Into the octahedral voids to form mixed spinels.
And, the invention also claims to be utilizedCobalt-based spinel Cu prepared by the method 0.7 Co 2.3 O 4 Use of an electrocatalyst in the electrocatalytic oxidation of glycerol.
Specifically, the prepared self-supporting catalyst is used as a working electrode, graphite is used as a counter electrode, hg/HgO is used as a reference electrode, and the three-electrode system is assembled for glycerol oxidation to produce formate.
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 0.3mol/L, and the concentration of the potassium hydroxide is 1mol/L.
Further, the glycerol in the mixed solution can be replaced by methanol, and the concentration is 0.3mol/L.
Compared with the prior art, the cobalt-based spinel Cu provided by the invention can be known through the technical scheme 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 prepare the catalyst with uniform sea urchin-like morphology, and the synthesis method is simple and suitable for large-scale production. Meanwhile, the catalyst exhibits excellent catalytic activity on glycerin. In the glycerol oxidation process of the catalyst, the voltage of only 1.17V (vs. RHE) is required to reach 10 mA cm -2 When reaching 400mA cm -2 At the industrial current density of (2), the required voltage is also only 1.37V (vs. RHE).
In addition, the catalyst also has excellent stability, and the catalyst has no obvious attenuation after the catalyst continuously runs for 60h under the potential of 1.4V (vs. RHE). This benefits from the introduction of copper ions and bulk migration, contributing to an increase in the intrinsic activity and stability of the catalyst. As shown in fig. 1, the X-ray diffraction pattern analysis chart demonstrates the successful introduction of copper element. FIG. 2 is a graph showing the high-resolution X-ray photoelectron spectrum of Cu2p at different calcination times, and it was confirmed by analyzing the peak area that migration of copper ions did occur inside the crystal. Studies have shown that hexacoordinated copper ions can produce Taylor distortion, resulting in increased structural asymmetry and thus reduced catalyst stability.
More importantly, compared with the anodic Oxygen Evolution Reaction (OER) in the water electrolysis reaction, the reaction voltage required by glycerol oxidation is significantly reduced (as shown in fig. 3), and the development space is wider.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
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) diagram of 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 test curve of catalyst material in mixed electrolyte of methanol and potassium hydroxide.
FIG. 6 is Cu prepared in example 1 and example 3 0.7 Co 2.3 O 4 Polarization curve (LSV) versus graph of catalyst material in a mixed electrolyte of glycerol and potassium hydroxide.
FIG. 7 is Cu prepared in example 1 0.7 Co 2.3 O 4 Polarization curve (LSV) plot of catalyst material in methanol and potassium hydroxide mixed electrolyte.
Detailed Description
The following description of embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The present invention will be further specifically illustrated by the following examples, which are not to be construed as limiting the invention, but rather as falling within the scope of the present invention, for some non-essential modifications and adaptations of the invention that are apparent to those skilled in the art based on the foregoing disclosure.
The technical scheme of the invention will be further described below with reference to specific embodiments.
Example 1
Self-supporting Cu 0.7 Co 2.3 O 4 The preparation method of the catalyst comprises the following specific steps:
and step 1, placing a commercial foamy copper substrate in a hydrochloric acid solution with the concentration of 1mol/L for ultrasonic treatment for 30min, and then sequentially flushing the foamy copper with ethanol and water for three times to remove oxide layers on the surface of the foamy copper and residual organic impurities in the production process.
Step 2, 1 mmol of cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·6H 2 O), 0.5 mmol copper nitrate trihydrate (Cu (NO) 3 ) 2 ·3H 2 O), 3 mmol of ammonium fluoride (NH) 4 F) And 6 mmol urea (CO (NH) 2 ) 2 ) Together dissolved in 30 mL deionized water and magnetically stirred for 30min to form homogeneous light pink solution.
Transferring the mixed solution into a 50 mL polytetrafluoroethylene lining stainless steel high-pressure hydrothermal kettle, adding pretreated foam copper, and putting into an oven, wherein the temperature is set to be 120 ℃ and the time is 12 h. And naturally cooling the hydrothermal kettle after the reaction is finished.
Step 3, taking out the material growing 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 6h; after the drying is finished, the material is calcined in a muffle furnace, the calcination time is set to be 1h, the calcination temperature is 300 ℃, and the heating rate is 2 ℃/min; the calcination is completed to obtain the cobalt copper spinel catalyst which uniformly grows on the substrate, and the X-ray diffraction diagram of the catalyst is shown in figure 1. The scanning electron microscope is shown in fig. 3.
Example 2
Electrochemical performance tests were performed using a conventional three-electrode system cell, and the catalytic activity of the catalyst was verified using an Shanghai Chenhua CHI 760E workstation.
Graphite as counter electrode, hg/HgO (1 mol/L KOH) as reference electrode, cu-loaded 0.7 Co 2.3 O 4 Copper foam of the catalyst was sheared into 1X 1 cm -2 The size was used as a working electrode, and the electrolyte was a mixed solution containing 0.3mol/L glycerol and 1mol/L KOH. Specifically, argon is used as circulating gas, argon is introduced for 30min before electrochemical test is started to remove impurity gas in electrolyte, CV activation is performed under the voltage range of 0-0.5V (vs. Hg/HgO), the scanning speed is 10 mV/s, the scanning turns are 20, and the activation of the catalyst is completed.
Then, a polarization curve test is performed, the voltage range is set to be 0-0.6V, the sweeping speed is 10 mV/s, the iR compensation is 85%, the result of the polarization curve is shown in FIG. 4, and the prepared Cu 0.7 Co 2.3 O 4 The catalyst shows excellent catalytic performance for glycerol oxidation. Reaching 10 mA cm -2 、100 mA·cm -2 And 400mA cm -2 The voltages required for the current densities were 1.17 and V, respectively RHE 、1.27 V RHE And 1.37V RHE Compared to the OER reaction, is reduced by more than 240 mV.
In addition, the tafel slope and impedance indicate catalyst Cu 0.7 Co 2.3 O 4 Has faster reaction kinetics and electron transfer speed. The improvement of the catalyst performance is based on the fact that the sea urchin-like morphology increases the exposure of the active sites and the contact area with the electrolyte, while the self-supporting material avoidsThe use of a binder reduces the charge transport resistance; on the other hand, the introduction of copper atoms changes the local environment of electrons, so that the intrinsic activity of the catalyst is improved.
The stability test was performed using a constant current curve, and the catalyst showed excellent durability at a voltage of 1.4V (vs. RHE) with little decay in catalytic activity 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 step 1, placing a commercial foamy copper substrate in a hydrochloric acid solution with the concentration of 1mol/L for ultrasonic treatment for 30min, and then sequentially flushing the foamy copper with ethanol and water for three times to remove oxide layers on the surface of the foamy copper and residual organic impurities in the production process.
Step 2, 1 mmol of cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·6H 2 O), 0.5 mmol copper nitrate trihydrate (Cu (NO) 3 ) 2 ·3H 2 O), 3 mmol of ammonium fluoride (NH) 4 F) And 6 mmol urea (CO (NH) 2 ) 2 ) Together dissolved in 30 mL deionized water and magnetically stirred for 30min to form homogeneous light pink solution.
Transferring the mixed solution into a 50 mL polytetrafluoroethylene lining stainless steel high-pressure hydrothermal kettle, adding pretreated foam copper, and putting into an oven, wherein the temperature is set to be 120 ℃ and the time is 12 h. And naturally cooling the hydrothermal kettle after the reaction is finished.
Step 3, taking out the material growing 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 6h; after the drying is finished, the material is calcined in a muffle furnace, the calcination time is set to be 2h, the calcination temperature is 300 ℃, and the heating rate is 2 ℃/min; and after the calcination is finished, the cobalt copper spinel catalyst which grows uniformly on the substrate is obtained.
Example 3 has a longer calcination time than example 1, and when the calcination time is prolonged, the Cu2p high fraction is shown according to FIG. 2As can be seen from the X-ray photoelectron spectrum, copper atoms with more tetrahedral gaps migrate into the octahedral gaps to form six-coordination, and according to researches, the six-coordination copper atoms are easy to generate Taylor distortion of ginger, so that the stability of a crystal structure is reduced, and the intrinsic activity of the catalyst is attenuated. In FIG. 2, cu Oh 2+ Represents copper atoms located in the octahedral gaps, cu Td 2+ Representing copper atoms located in tetrahedral interstices. Cu (Cu) 0.7 Co 2.3 O 4 -1 represents a calcination time of 1h, cu 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 is partially collapsed, resulting in a decrease in exposed catalytic active sites, further decreasing the catalytic activity of the catalyst.
Example 4
The electrochemical performance test is carried out by using a conventional three-electrode electrolytic cell, and the catalytic activity of the catalyst is verified by using the Shanghai Chenhua CHI 760E workstation.
Graphite as a counter electrode, hg/HgO (1 mol/L KOH) as a reference electrode, and copper foam carrying the catalyst prepared in example 3 was cut into 1X 1 cm -2 The size was used as a working electrode, and the electrolyte was a mixed solution containing 0.3mol/L glycerol and 1mol/L KOH. Specifically, argon is used as circulating gas, argon is introduced for 30min before electrochemical test is started to remove impurity gas in electrolyte, CV activation is performed under the voltage range of 0-0.5V (vs. Hg/HgO), the scanning speed is 10 mV/s, the scanning turns are 20, and the activation of the catalyst is completed.
Then, a polarization curve test was performed, the voltage range was set to 0 to 0.6V, the sweep rate was 10 mV/s, the iR compensation was 85%, and the result of the polarization curve was shown in FIG. 6, and the catalytic activity of example 3 was reduced compared with that of example 1. This is due to the collapse of the catalyst morphology reducing the exposure of the active sites and the excessive migration of copper atoms inside the crystal reducing the stability of the catalyst.
Example 5
The electrochemical performance test is carried out by using a conventional three-electrode electrolytic cell, and the catalytic activity of the catalyst is verified by using the Shanghai Chenhua CHI 760E workstation.
Graphite as counter electrode, hg/HgO (1 mol/L KOH) as reference electrode, cu-loaded 0.7 Co 2.3 O 4 Copper foam of the catalyst was sheared into 1X 1 cm -2 The size was used as a working electrode, and the electrolyte was a mixed solution containing 0.3mol/L methanol and 1mol/L KOH. Specifically, argon is used as circulating gas, argon is introduced for 30min before electrochemical test is started to remove impurity gas in electrolyte, CV activation is performed under the voltage range of 0-0.5V (vs. Hg/HgO), the scanning speed is 10 mV/s, the scanning turns are 20, and the activation of the catalyst is completed.
Then, a polarization curve test is carried out, the voltage range is set to be 0-0.6V, the sweeping speed is 10 mV/s, the iR compensation is 85%, 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. Reaching 10 mA cm -2 、100 mA·cm -2 And 400mA cm -2 The voltages required for the current densities were 1.17 and V, respectively RHE 、1.27 V RHE And 1.37V RHE Compared to the OER reaction, is reduced by more than 240 mV.
In addition, the tafel slope and impedance indicate catalyst Cu 0.7 Co 2.3 O 4 Has faster reaction kinetics and electron transfer speed. On one hand, the catalyst performance is improved because the sea urchin-shaped morphology increases the exposure of active sites and the contact area between the active sites and 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 synergy between the bimetallic catalysts changes the electronic local environment, thereby improving the intrinsic activity of the catalyst.
Example 5 substitution of glycerol in electrolyte with methanol, the same excellent electrochemical performance after polarization Curve test using electrochemical workstation was achieved to 400mA cm -2 The voltage required for the current density was 1.51V (vs. RHE), and the result is shown in fig. 7.
The overpotential required for the electrooxidation of methanol is relatively large compared to the electrooxidation of glycerol, on the one hand because glycerol is a three-molecule hydroxyl alcohol, glycerol and methanol of the same concentration, glycerol has a richer number of hydroxyl groups, and on the other hand because methanol is a primary alcohol, which contains primary and secondary alcohols, which react more easily 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 (2)
1. Cobalt-based spinel Cu 0.7 Co 2.3 O 4 Use of an electrocatalyst for the electrocatalytic oxidation of glycerol to formate, characterized in that said spinel Cu 0.7 Co 2.3 O 4 The preparation method of the electrocatalyst comprises the following steps:
1) Placing a commercial foam copper substrate in a hydrochloric acid solution with the concentration of 1-3 mol/L for ultrasonic treatment for 30-60 min, and then sequentially flushing the foam copper with ethanol and water for three times to remove an oxide layer and residual organic impurities on the surface of the foam copper for later use;
2) Cobalt salt, copper salt, ammonium fluoride and urea are weighed and dissolved in deionized water together, and after magnetic stirring is carried out for 15-30 min, a uniform light pink mixed solution is formed;
3) Transferring the mixed solution obtained in the step 2) into a polytetrafluoroethylene lining stainless steel high-pressure hydrothermal kettle, simultaneously adding foam copper pretreated in the step 1), putting into an oven, setting the temperature to 120 ℃ for 6-12 h, and naturally cooling the hydrothermal kettle after the reaction is finished;
4) Taking out the material growing with the precursor catalyst from the hydrothermal kettle, repeatedly washing the material with deionized water, and then placing the material into a 70 ℃ oven for drying for 6 hours; after the drying is finished, calcining the material in a muffle furnace for 1h at a calcining temperature of 300 ℃ at a heating rate of 2 ℃/min; after the calcination is finished, a cobalt copper spinel catalyst which grows uniformly on the substrate is obtained;
the Cu is 0.7 Co 2.3 O 4 The electrocatalyst has a sea urchin-like structure, the size is between 7 and 13 mu m, and the diameter of sea urchin thorns is smaller than 100mm;
the cobalt salt is cobalt nitrate hexahydrate, and the copper salt is copper nitrate trihydrate;
the mole ratio of the cobalt nitrate hexahydrate, the copper nitrate trihydrate, the ammonium fluoride and the urea is 1:0.5:3:6, after the cobalt salt is dissolved in deionized water, the concentration range is 0.025-0.035 mol/L;
the application specifically operates as follows:
cu of the cobalt-based spinel 0.7 Co 2.3 O 4 The electrocatalyst is used as a working electrode, graphite is used as a counter electrode, hg/HgO is used as a reference electrode, and the three-electrode system is assembled for glycerol oxidation to produce formate;
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 0.3mol/L, and the concentration of the potassium hydroxide is 1mol/L.
2. Use according to claim 1, characterized in that the glycerol in the mixed solution is replaced by methanol at a concentration of 0.3mol/L.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489301A (en) * | 2011-11-24 | 2012-06-13 | 北京化工大学 | Structured copper-cobalt based catalyst and application of catalytic synthesis gas of structured copper-cobalt based catalyst in preparation of higher alcohols |
| CN102641736A (en) * | 2012-03-19 | 2012-08-22 | 中国科学院过程工程研究所 | Sea urchin shaped copper oxide catalyst, as well as preparation method and application thereof |
| CN108796551A (en) * | 2018-06-04 | 2018-11-13 | 佛山市利元合创科技有限公司 | It is supported on sea urchin shape vulcanization Co catalysts in nickel foam and preparation method thereof, as the application of electrolysis water oxygen-separating catalyst |
| CN111672530A (en) * | 2020-05-19 | 2020-09-18 | 江苏大学 | Preparation method of CuCo-N/C nano catalyst and application of CuCo-N/C nano catalyst in preparing lactic acid by catalytic oxidation of 1, 2-propylene glycol |
| CN113235125A (en) * | 2021-05-18 | 2021-08-10 | 上海大学 | Nickel-based NiCo2O4Electrocatalyst and its use in electrocatalytic oxidation of glycerol |
| CN113718290A (en) * | 2021-09-07 | 2021-11-30 | 北京化工大学 | Cu-CuS/BM electrode material for preparing formate by electrocatalytic oxidation of glycerol and preparation method thereof |
-
2023
- 2023-02-06 CN CN202310067542.XA patent/CN115786964B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489301A (en) * | 2011-11-24 | 2012-06-13 | 北京化工大学 | Structured copper-cobalt based catalyst and application of catalytic synthesis gas of structured copper-cobalt based catalyst in preparation of higher alcohols |
| CN102641736A (en) * | 2012-03-19 | 2012-08-22 | 中国科学院过程工程研究所 | Sea urchin shaped copper oxide catalyst, as well as preparation method and application thereof |
| CN108796551A (en) * | 2018-06-04 | 2018-11-13 | 佛山市利元合创科技有限公司 | It is supported on sea urchin shape vulcanization Co catalysts in nickel foam and preparation method thereof, as the application of electrolysis water oxygen-separating catalyst |
| CN111672530A (en) * | 2020-05-19 | 2020-09-18 | 江苏大学 | Preparation method of CuCo-N/C nano catalyst and application of CuCo-N/C nano catalyst in preparing lactic acid by catalytic oxidation of 1, 2-propylene glycol |
| CN113235125A (en) * | 2021-05-18 | 2021-08-10 | 上海大学 | Nickel-based NiCo2O4Electrocatalyst and its use in electrocatalytic oxidation of glycerol |
| CN113718290A (en) * | 2021-09-07 | 2021-11-30 | 北京化工大学 | Cu-CuS/BM electrode material for preparing formate by electrocatalytic oxidation of glycerol and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Cations distribution of CuxCo3-xO4 and its electrocatalytic activities for oxygen evolution reaction;Bo Chi;International Journal Of Hydrogen Energy;第33卷;4763-4768 * |
| Electrocatalytic Oxidation of Glycerol to Formic Acid by CuCo2O4 Spinel Oxide Nanostructure Catalysts;Xiaotong Han;ACS Catalysis;第10卷;6741-6752 * |
| MgCo2O4海胆状电极材料的制备及其电化学性能;倪航等;材料工程;第50卷(第50期);143-152 * |
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