CN115094439A - Cerium oxide modified cobalt diselenide catalyst and preparation method and application thereof - Google Patents
Cerium oxide modified cobalt diselenide catalyst and preparation method and application thereof Download PDFInfo
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- CN115094439A CN115094439A CN202210809477.9A CN202210809477A CN115094439A CN 115094439 A CN115094439 A CN 115094439A CN 202210809477 A CN202210809477 A CN 202210809477A CN 115094439 A CN115094439 A CN 115094439A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- -1 Cerium oxide modified cobalt diselenide Chemical class 0.000 title claims abstract description 42
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 46
- 239000004744 fabric Substances 0.000 claims abstract description 45
- 150000001868 cobalt Chemical class 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 150000000703 Cerium Chemical class 0.000 claims abstract description 19
- HQFBUALMHFGXCO-UHFFFAOYSA-N cerium oxocobalt Chemical compound [Ce].[Co]=O HQFBUALMHFGXCO-UHFFFAOYSA-N 0.000 claims abstract description 18
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 claims abstract description 16
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 15
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 15
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 230000001681 protective effect Effects 0.000 claims abstract description 6
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 6
- 238000004321 preservation Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- XFRXMMOAPQQZPY-UHFFFAOYSA-K azanium cerium(3+) disulfate hydrate Chemical compound O.S(=O)(=O)([O-])[O-].[NH4+].[Ce+3].S(=O)(=O)([O-])[O-] XFRXMMOAPQQZPY-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract 1
- GAIMSHOTKWOMOB-UHFFFAOYSA-N [Se]=[Co]=[Se] Chemical compound [Se]=[Co]=[Se] GAIMSHOTKWOMOB-UHFFFAOYSA-N 0.000 description 11
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 8
- 239000010411 electrocatalyst Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000005660 hydrophilic surface Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010351 charge transfer process Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a cerium oxide modified cobalt diselenide catalyst and a preparation method and application thereof, wherein the preparation method of the cerium oxide modified cobalt diselenide catalyst comprises the following steps: placing the carbon cloth in a mixed solution of soluble cobalt salt and soluble cerium salt, and carrying out hydrothermal reaction to obtain carbon cloth coated by cobalt hydroxide and cerium hydroxide; keeping the temperature of the carbon cloth coated with the cobalt hydroxide and the cerium hydroxide in a protective atmosphere to obtain cerium cobalt oxide; and placing the cerium-cobalt oxide and selenium powder in a double-temperature-zone tubular furnace, and preserving heat in a reducing atmosphere, wherein the selenium powder is located in an upstream zone at 300-375 ℃, the cerium-cobalt oxide is located in a downstream zone at 300-500 ℃, and a product prepared in the downstream zone after heat preservation is finished is the catalyst. The catalyst prepared by the invention has excellent electrochemical activity on the anodic oxygen evolution reaction of the electrolyzed water under the alkaline condition, greatly reduces the voltage required by the anodic reaction, reduces the energy consumption of the electrolyzed water, and improves the hydrogen production efficiency of the electrolyzed water.
Description
Technical Field
The invention belongs to the technical field of electrocatalysts, and particularly relates to a cerium oxide modified cobalt diselenide catalyst, and a preparation method and application thereof.
Background
The use of fossil fuels in large quantities brings serious energy crisis and environmental pollution, people are prompted to attach high importance to the development of renewable energy, and hydrogen energy is widely concerned by people due to cleanness, no pollution and high combustion value. The water electrolysis hydrogen production technology has the advantages of simple device, high product purity and less secondary pollution, and is considered to be one of the most ideal hydrogen production technologies. Electrolyzed water consists of two half-reactions: hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER). However, the OER process needs to overcome the high reaction energy barrier, the slow reaction kinetics and the coupling problems of multiple proton and electron transfers, and thus, OER determines the overall water splitting efficiency. RuO to date 2 And IrO 2 Is considered to be the electrocatalyst with the highest OER activity. However, their large-scale application is severely hampered by high cost and resource shortage. Therefore, the development of economical and effective non-noble metal electrocatalysts has attracted great interest to researchers.
In recent years, cobalt-based metal compound electrocatalysts have the characteristics of excellent oxidation-reduction performance, low cost and the like due to the cobalt element, so that the cobalt-based metal compound electrocatalysts become ideal materials for constructing electrocatalytic oxygen production catalysts with high efficiency and low cost. Wherein, CoSe 2 As a typical cobalt-based metal compound, the cobalt-based metal compound has a unique local metal bonding structure, obvious metal characteristics and high conductivity, and shows wide application prospects in an electrolytic water oxygen evolution reaction. Although the high conductivity of transition metal selenides makes them excellent electrocatalysts, there is still a need to further improve their water-splitting performance. Doping elements or making defect structures have proven to be an effective way to further increase the intrinsic activity of the catalyst towards OER by adjusting the electronic structure and optimizing the intermediate absorption energy. Recently, cerium oxide, a transition metal oxide, has been abundant in oxygen vacancy defects and Ce 3+ And Ce 4+ Flexible conversion between states and the like, so that the catalyst becomes a hot material in the field of catalysis. However, the controllability of defects in manufacturing is poor and the electron conductivity is reduced. In recent years, both theoretical and experimental studies show that the OER electrocatalytic performance of the transition metal catalyst can be greatly improved by doping hetero atoms. The doping can adjust the electronic structure, increase the active sites and improveConductivity, accelerated kinetics and optimized adsorption/desorption energy of intermediates. Based on these studies, it can be reasonably hypothesized that doping cerium oxide into an electrocatalyst would be an effective method to improve the water-splitting electrocatalytic performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a cerium oxide modified cobalt diselenide catalyst and a preparation method and application thereof. The catalyst has high catalytic activity, the doping of cerium oxide enables the catalyst to expose more oxygen vacancy defects, the precipitation of oxygen is accelerated, and the generation of oxygen evolution reaction is facilitated, so that the overpotential of anode oxygen evolution reaction is reduced, the catalyst has excellent conductivity, and the hydrogen production efficiency of cobalt diselenide electrolysis water is greatly improved.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a cerium oxide modified cobalt diselenide catalyst comprises the following steps:
(1) placing the carbon cloth in a mixed solution of soluble cobalt salt and soluble cerium salt, and carrying out hydrothermal reaction at 100-180 ℃ to obtain carbon cloth coated with cobalt hydroxide and cerium hydroxide;
(2) preserving the heat of the carbon cloth coated with the cobalt hydroxide and the cerium hydroxide in the step (1) for 1-3 hours at 300-450 ℃ in a protective atmosphere to obtain cerium-cobalt oxide; the step is to remove part of crystal water;
(3) and (3) placing the cerium-cobalt oxide and the selenium powder in the step (2) in a double-temperature-zone tube furnace, and preserving heat for 1-2 hours in a hydrogen atmosphere, wherein the selenium powder is located in an upstream zone at 300-375 ℃, the cerium-cobalt oxide is located in a downstream zone at 300-500 ℃, and a product prepared in the downstream zone after heat preservation is finished is the cerium oxide modified cobalt diselenide catalyst.
Preferably, the carbon cloth in the step (1) is pretreated before use as follows: heating the carbon cloth to 600-700 ℃ to remove oily substances on the surface of the carbon cloth, and then ultrasonically cleaning the carbon cloth by using deionized water to remove residual impurities on the surface of the carbon cloth.
Preferably, the mixed solution of cobalt salt and cerium salt in the step (1) is prepared by the following steps: adding soluble cobalt salt, soluble cerium salt and urea into water, and stirring until the soluble cobalt salt, the soluble cerium salt and urea are completely dissolved, wherein the concentration of the soluble cobalt salt is 0.01-0.34 mol/L, and the molar ratio of the soluble cobalt salt to the soluble cerium salt is 2-50: 1; the concentration of the urea is 1.67 mol/L.
Preferably, the hydrothermal reaction time in the step (1) is 6-12 h.
Preferably, the soluble cobalt salt in step (1) is at least one of cobalt sulfate, cobalt nitrate and cobalt acetate.
Preferably, the soluble cerium salt in step (1) is at least one of cerium nitrate, ammonium cerium sulfate hydrate and cerium sulfate.
Preferably, the protective atmosphere in the step (2) is N 2 And Ar.
Preferably, the dosage of the selenium powder in the step (3) is not less than 60% of the molar weight of the soluble cobalt salt in the step (1).
Preferably, the reducing atmosphere in step (3) is hydrogen.
The cerium oxide modified cobalt diselenide catalyst prepared by the preparation method of the cerium oxide modified cobalt diselenide catalyst is provided.
The cerium oxide modified cobalt diselenide catalyst is applied to preparation of an electrocatalytic oxygen evolution material.
The reaction mechanism of the invention is as follows: obtaining cobalt hydroxide and cerium hydroxide precursors which grow uniformly on carbon cloth by utilizing a hydrothermal reaction, removing part of crystal water contained in the precursors (beneficial to the implementation of selenization reaction) by high-temperature heat treatment in a protective atmosphere to obtain cerium-cobalt oxide, and finally synthesizing a target product by adopting a chemical vapor deposition method in a reducing atmosphere: a cerium oxide modified cobalt diselenide catalyst.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a cerium oxide modified cobalt diselenide catalyst and a preparation method and application thereof, the catalyst has high catalytic activity, the doping of cerium oxide enables the catalyst to expose more oxygen vacancy defects, the precipitation of oxygen is accelerated, and the oxygen evolution reaction is facilitated, so that the overpotential of the anode oxygen evolution reaction is reduced, the electrode surface charge transfer dynamics is accelerated, the catalytic reaction rate is accelerated, and the hydrogen production efficiency of cobalt diselenide by electrolysis is further improved.
Drawings
Fig. 1 is an X-ray diffraction XRD pattern of the ceria modified cobalt diselenide catalyst prepared in example 1.
Fig. 2 is a graph comparing oxygen evolution performance tests of the ceria modified cobalt diselenide catalyst material prepared in example 1 and cobalt diselenide.
Fig. 3 is a comparison graph of electrochemical impedance spectroscopy tests of the ceria modified cobalt diselenide catalyst material prepared in example 1 and cobalt diselenide.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The carbon cloth described in the examples is available from CoTech technologies, inc, WOS 1009.
Example 1
A preparation method of a cerium oxide modified cobalt diselenide catalyst comprises the following steps:
(1) firstly, pretreating the carbon cloth: placing a carbon cloth with the size of 1cm multiplied by 3cm in a tubular furnace, heating to 600 ℃ in the air, preserving the heat for 30min to remove a coating with a non-hydrophilic surface, then carrying out ultrasonic treatment on the carbon cloth for 30min by using deionized water, and then cleaning to remove residual impurities on the surface of the carbon cloth;
(2) adding 0.01mol of cobalt nitrate, 0.001mol of cerium nitrate and 0.05mol of urea into 30mL of deionized water, stirring for 30min to obtain a mixed solution of cobalt salt and cerium salt, putting the carbon cloth pretreated in the step (1) into the mixed solution of cobalt salt and cerium salt, carrying out hydrothermal reaction at 120 ℃ for 6 h, growing on the carbon cloth to obtain cobalt hydroxide and cerium hydroxide, washing the carbon cloth coated with the cobalt hydroxide and cerium hydroxide for 2-3 times by using the deionized water and absolute ethyl alcohol, and drying in a blast drying box at 60 ℃ for later use;
(3) the hydrogen dried in the step (2) is oxidizedPlacing the carbon cloth coated with cobalt and cerium hydroxide in a tubular furnace for heat treatment, wherein the heat treatment parameters are as follows: keeping the temperature at 300 ℃ for 3 hours, wherein the atmosphere in the furnace is N 2 The flow rate was 50 sccm. Obtaining cerium cobalt oxide after heat treatment;
(4) and (4) placing the cerium cobalt oxide subjected to the heat treatment in the step (3) in a double-temperature-zone tube furnace for selenylation reaction for 1 hour. The reaction parameters are set as follows: 0.5g of selenium powder is placed in the upstream area for 75 minutes, the temperature is raised to 375 ℃, and the temperature is kept for 1 hour; placing cerium-cobalt oxide in a downstream area, heating to 400 ℃ in 80 minutes and preserving heat for 1 hour; atmosphere in the furnace is H 2 The flow rate was 60 sccm. And after the reaction is finished, the substance prepared in the downstream region is the cerium oxide modified cobalt diselenide catalyst.
Selenium powder was excessive in this reaction, and it was apparent that there was residue after the reaction. And the cobalt ions in the hydrothermal solution in the step (2) are not completely loaded on the carbon cloth.
The X-ray diffraction XRD of the cerium oxide modified cobalt diselenide catalyst material prepared in example 1 is shown in fig. 1. Compared with an XRD standard card database, the synthetic material corresponds to cerium oxide (PDF #34-0394) and cobalt diselenide (PDF #53-0449) one by one, which shows that the cerium oxide modified cobalt diselenide catalyst is successfully synthesized.
Fig. 2 is a graph comparing oxygen evolution performance tests of the ceria modified cobalt diselenide catalyst material prepared in example 1 and cobalt diselenide. The specific test conditions are based on a three-electrode electrochemical system, the electrochemical workstation is a Shanghai Huachi 660e electrochemical workstation, the reference electrode is a saturated calomel electrode, the counter electrode is a carbon rod, the working electrode is a catalyst sample fixed by a platinum clamp (the sample is respectively the cerium oxide modified cobalt diselenide catalyst material prepared in the example 1 and pure cobalt diselenide), the size of the sample is 0.6cm multiplied by 0.8cm, and the sample is placed in a 1.0M KOH electrolyte for electrochemical oxygen evolution performance test. The test potential range is 0-1.0V, and the scanning speed is 5 mV/s. As can be seen from fig. 2: at a current density of 50mA cm -2 Compared with pure-phase cobalt diselenide, the overpotential of the cobalt diselenide catalyst modified by cerium oxide is reduced by 160mV, which shows that the oxygen evolution reaction is easier to occur at the moment, and proves that the doped cerium oxide has the promotion effect on the catalytic reactionThe application is as follows.
Fig. 3 is a comparison graph of electrochemical impedance spectroscopy tests of the ceria modified cobalt diselenide catalyst material of example 1 and cobalt diselenide. Electrochemical Impedance Spectroscopy (EIS) is used to characterize electrode surface kinetics. The semicircle of the high frequency region represents the charge transfer process, the diameter of the semicircle is a resistance value, and the smaller the charge transfer resistance is, the faster the reaction rate is. As can be seen from fig. 3: after the cerium oxide is added for modification, the resistance value of the composite material is obviously reduced, which shows that the charge transfer kinetics of the electrode material is accelerated, and the catalytic reaction rate is accelerated. The specific test conditions are based on a three-electrode electrochemical system, the electrochemical workstation is a Shanghai Huachi 660e electrochemical workstation, the reference electrode is a saturated calomel electrode, the counter electrode is a carbon rod, the working electrode is a catalyst sample fixed by a platinum clamp (the sample is respectively the cerium oxide modified cobalt diselenide catalyst material prepared in example 1 and pure cobalt diselenide), the size of the sample is 0.6cm multiplied by 0.8cm, and the sample is placed in 1.0M KOH electrolyte for electrochemical impedance test. The test potential was 0.45V, the high frequency was 100000Hz, the low frequency was 0.1Hz, and the amplitude was 0.005V.
Example 2
A preparation method of a cerium oxide modified cobalt diselenide catalyst comprises the following steps:
(1) firstly, pretreating the carbon cloth: placing the carbon cloth in a tube furnace, heating to 650 ℃ in the air, preserving heat for 20min to remove the coating with non-hydrophilic surface, then carrying out ultrasonic treatment for 30min by using deionized water, and then cleaning to remove the residual impurities on the surface of the carbon cloth;
(2) adding 0.005mol of cobalt nitrate, 0.0002mol of cerium nitrate and 0.05mol of urea into 30mL of deionized water, stirring for 30min to obtain a mixed solution of cobalt salt and cerium salt, putting the carbon cloth pretreated in the step (1) into the mixed solution of cobalt salt and cerium salt, carrying out hydrothermal reaction at 100 ℃ for 10 hours, growing on the carbon cloth to obtain cobalt hydroxide and cerium hydroxide, washing the carbon cloth coated with the cobalt hydroxide and the cerium hydroxide for 2-3 times by using the deionized water and absolute ethyl alcohol, and drying in a blast drying box at 60 ℃ for later use;
(3) placing the carbon cloth coated with the cobalt hydroxide and the cerium hydroxide dried in the step (2) in a tubular formCarrying out heat treatment in a furnace, wherein the heat treatment temperature parameters are set as follows: keeping the temperature at 450 ℃ for 1 hour, wherein the atmosphere condition in the furnace is N 2 At a flow rate of 50 sccm. Obtaining cerium cobalt oxide after heat treatment;
(4) and (4) placing the cerium-cobalt oxide subjected to the heat treatment in the step (3) in a double-temperature-zone tube furnace for selenylation reaction for 2 hours. The reaction parameters are set as follows: placing 0.5g of selenium powder in an upstream area, heating to 300 ℃ within 55 minutes, and keeping the temperature for 2 hours; the cerium-cobalt oxide is placed in the downstream area, and the temperature is raised to 300 ℃ for 60 minutes and kept for 2 hours. The atmosphere in the furnace is H 2 The flow rate was 60 sccm. And after the reaction is finished, the substance prepared in the downstream region is the cerium oxide modified cobalt diselenide catalyst.
Example 3
A preparation method of a cerium oxide modified cobalt diselenide catalyst comprises the following steps:
(1) firstly, pretreating the carbon cloth: placing the carbon cloth in a tube furnace, heating to 700 ℃ in the air, preserving heat for 10min to remove the non-hydrophilic coating on the surface, then carrying out ultrasonic treatment for 30min by using deionized water, and cleaning to remove residual impurities on the surface of the carbon cloth;
(2) adding 0.001mol of cobalt nitrate, 0.0005mol of cerium nitrate and 0.05mol of urea into 30mL of deionized water, stirring for 30min to obtain a mixed solution of cobalt salt and cerium salt, putting the carbon cloth pretreated in the step (1) into the mixed solution of cobalt salt and cerium salt, carrying out hydrothermal reaction at 180 ℃ for 4 hours, growing on the carbon cloth to obtain cobalt hydroxide and cerium hydroxide, washing the carbon cloth coated with the cobalt hydroxide and cerium hydroxide for 2-3 times by using the deionized water and absolute ethyl alcohol, and drying in a blast drying box at 60 ℃ for later use;
(3) and (3) placing the carbon cloth coated with the cobalt hydroxide and the cerium hydroxide dried in the step (2) in a tubular furnace for heat treatment, wherein the heat treatment temperature parameters are as follows: keeping the temperature at 400 ℃ for 2 hours under the furnace atmosphere condition of N 2 At a flow rate of 50 sccm. Obtaining cerium cobalt oxide after heat treatment;
(4) and (4) placing the cerium-cobalt oxide carbon cloth subjected to heat treatment in the step (3) in a double-temperature-zone tube furnace for selenylation reaction for 1 h. The reaction parameters are set as follows: placing 0.5g of selenium powder in an upstream area, heating to 500 ℃ within 95 minutes, and keeping the temperature for 1 hour; the cerium-cobalt oxide is placed in the downstream area,the temperature was raised to 500 ℃ over 100 minutes and held for 1 hour. The atmosphere in the furnace is H 2 The flow rate was 60 sccm. And after the reaction is finished, the substance prepared in the downstream region is the cerium oxide modified cobalt diselenide catalyst.
The oxygen evolution performance and electrochemical impedance spectra of the ceria modified cobalt diselenide catalysts prepared in examples 2 and 3 were similar to those of example 1.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a cerium oxide modified cobalt diselenide catalyst is characterized by comprising the following steps:
(1) placing the carbon cloth in a mixed solution of soluble cobalt salt and soluble cerium salt, and carrying out hydrothermal reaction at 100-180 ℃ to obtain carbon cloth coated with cobalt hydroxide and cerium hydroxide;
(2) preserving the temperature of the cobalt hydroxide and cerium hydroxide coated carbon cloth in the step (1) for 1-3 h at 300-450 ℃ in a protective atmosphere to obtain cerium cobalt oxide;
(3) and (3) placing the cerium-cobalt oxide and the selenium powder in the step (2) in a double-temperature-zone tube furnace, and preserving heat for 1-2 hours in a reducing atmosphere, wherein the selenium powder is located in an upstream zone at 300-375 ℃, the cerium-cobalt oxide is located in a downstream zone at 300-500 ℃, and a product prepared in the downstream zone after heat preservation is finished is the cerium oxide modified cobalt diselenide catalyst.
2. The method for preparing a cerium oxide modified cobalt diselenide catalyst according to claim 1, wherein the mixed solution of the cobalt salt and the cerium salt in the step (1) is prepared by the following steps: adding soluble cobalt salt, soluble cerium salt and urea into water, and stirring until the soluble cobalt salt, the soluble cerium salt and urea are completely dissolved, wherein the concentration of the soluble cobalt salt is 0.01-0.34 mol/L, and the molar ratio of the soluble cobalt salt to the soluble cerium salt is 2-50: 1; the concentration of the urea is 1.67 mol/L.
3. The method for preparing a cerium oxide modified cobalt diselenide catalyst according to claim 1, wherein the selenium powder in the step (3) is used in an amount of not less than 60% by mole of the soluble cobalt salt in the step (1).
4. The method for preparing a cerium oxide modified cobalt diselenide catalyst according to any one of claims 1 to 3, wherein the carbon cloth of the step (1) is pretreated before use as follows: heating the carbon cloth to 600-700 ℃ to remove oily substances on the surface of the carbon cloth, and then ultrasonically cleaning the carbon cloth by using deionized water to remove residual impurities on the surface of the carbon cloth.
5. The preparation method of the cerium oxide modified cobalt diselenide catalyst according to claim 4, wherein the hydrothermal reaction time in the step (1) is 6-12 hours.
6. The method for preparing a cerium oxide modified cobalt diselenide catalyst according to any one of claims 1 to 3, wherein the soluble cobalt salt in the step (1) is at least one of cobalt sulfate, cobalt nitrate and cobalt acetate.
7. The method of claim 6, wherein the soluble cerium salt in step (1) is at least one of cerium nitrate, ammonium cerium sulfate hydrate, and cerium sulfate.
8. The preparation method of the cerium oxide modified cobalt diselenide catalyst according to any one of claims 1 to 3, wherein the protective atmosphere in the step (2) is N 2 And Ar;
and (3) the reducing atmosphere is hydrogen.
9. The cerium oxide modified cobalt diselenide catalyst prepared by the preparation method of the cerium oxide modified cobalt diselenide catalyst according to any one of claims 1 to 8.
10. Use of the cerium oxide modified cobalt diselenide catalyst of claim 9 in the preparation of an electrocatalytic oxygen evolution material.
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