CN115094439B - 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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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 43
- -1 Cerium oxide modified cobalt diselenide Chemical class 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 45
- 239000004744 fabric Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 150000001868 cobalt Chemical class 0.000 claims abstract description 22
- 150000000703 Cerium Chemical class 0.000 claims abstract description 18
- HQFBUALMHFGXCO-UHFFFAOYSA-N cerium oxocobalt Chemical compound [Ce].[Co]=O HQFBUALMHFGXCO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 16
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 claims abstract description 16
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 16
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 6
- 238000004321 preservation Methods 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 14
- GAIMSHOTKWOMOB-UHFFFAOYSA-N [Se]=[Co]=[Se] Chemical class [Se]=[Co]=[Se] GAIMSHOTKWOMOB-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 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
- 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 1
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract 1
- 239000010411 electrocatalyst Substances 0.000 description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000012546 transfer Methods 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
- 238000005516 engineering process Methods 0.000 description 3
- 230000005660 hydrophilic surface Effects 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte 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
- 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
- KFVLFWWLSIOANK-UHFFFAOYSA-N cerium cobalt Chemical compound [Co].[Co].[Co].[Co].[Co].[Ce] KFVLFWWLSIOANK-UHFFFAOYSA-N 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development 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
- 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
- 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
Classifications
-
- 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 carbon cloth in a mixed solution of soluble cobalt salt and soluble cerium salt, and performing hydrothermal reaction to obtain cobalt hydroxide and cerium hydroxide coated carbon cloth; preserving heat of cobalt hydroxide and cerium hydroxide coated carbon cloth in a protective atmosphere to obtain cerium cobalt oxide; and (3) placing cerium-cobalt oxide and selenium powder in a double-temperature-zone tube furnace, preserving heat in a reducing atmosphere, wherein the selenium powder is positioned in an upstream zone of 300-375 ℃, the cerium-cobalt oxide is positioned in a downstream zone of 300-500 ℃, and the product prepared in the downstream zone after the heat preservation is finished is the catalyst. The catalyst prepared by the invention has excellent electrochemical activity on the electrolytic water anode oxygen evolution reaction under alkaline conditions, greatly reduces the voltage required by the anode reaction, reduces the electrolytic water energy consumption and improves the electrolytic water hydrogen production efficiency.
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 large-scale use of fossil fuels brings serious energy crisis and environmental pollution, and brings great importance to the development of renewable energy sources, and hydrogen energy is widely focused by people because of clean and pollution-free combustion values. The water electrolysis hydrogen production technology has simple device, high product purity and less secondary pollution, and is considered as 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, OER processes need to overcome the problems of high reaction energy barriers, slow reaction kinetics and coupling of multiple proton and electron transfer, and thus OER determines the efficiency of the overall water decomposition. To date, ruO 2 And IrO 2 Is considered to be the most active electrocatalyst for OER. However, their large-scale application is severely hampered by high costs and resource shortages. Therefore, there is great interest among researchers in developing cost-effective non-noble metal electrocatalysts.
In recent years, cobalt-based metal compound electrocatalyst is an ideal material for constructing high-efficiency low-cost electrocatalyst oxygen production catalyst because of the characteristics of excellent oxidation-reduction performance, low cost and the like of cobalt element. Wherein, coSe 2 As a typical cobalt-based metal compound, the cobalt-based metal compound has a unique local metal bonding structure, remarkable metal characteristics and higher conductivity, and has wide application prospect in electrolytic water oxygen evolution reaction. Although the high conductivity of the transition metal selenide makes it an excellent electrocatalyst, there is still a need to further improve its water splitting properties. Doping elements or fabricating defective structures have proven to be effective methods for further increasing the inherent activity of the catalyst towards OER by adjusting the electronic structure and optimizing the intermediate absorption energy. In recent years, cerium oxide has been used as a transition metal oxide and has abundant oxygen vacancy defects and Ce 3+ And Ce (Ce) 4+ Flexible conversion between states, etc., which makes it a hot spot material in the catalytic field. However, the defect controllability of the manufacture is poor and the electron conductivity is lowered. 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 site, improve the conductivity, accelerate the dynamics and optimize the adsorption/desorption energy of the intermediate. Based on these studies, it can be reasonably assumed that doping cerium oxide into an electrocatalyst would be an effective method to improve the water-splitting electrocatalyst performance.
Disclosure of Invention
Aiming at overcoming 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, and the doping of cerium oxide enables the catalyst to expose more oxygen vacancy defects, accelerates the precipitation of oxygen, and is beneficial to the occurrence of oxygen precipitation reaction, thereby reducing the overpotential of the anode oxygen precipitation reaction, having excellent conductivity and greatly improving the hydrogen production efficiency of the electrolytic water of cobalt diselenide.
The aim of the invention is achieved by the following technical scheme:
a method for preparing a cerium oxide modified cobalt diselenide catalyst, which comprises the following steps:
(1) Placing carbon cloth in a mixed solution of soluble cobalt salt and soluble cerium salt, and performing hydrothermal reaction at 100-180 ℃ to obtain cobalt hydroxide and cerium hydroxide coated carbon cloth;
(2) The cobalt hydroxide and the carbon cloth coated by the cerium hydroxide in the step (1) are kept at 300-450 ℃ for 1-3 hours under the protection atmosphere, so as to obtain cerium cobalt oxide; this step is to remove part of the crystal water;
(3) And (3) placing the cerium-cobalt oxide and the selenium powder obtained in the step (2) into a double-temperature zone tube furnace, and preserving the heat for 1-2 h in a hydrogen atmosphere, wherein the selenium powder is positioned in an upstream zone of 300-375 ℃, the cerium-cobalt oxide is positioned in a downstream zone of 300-500 ℃, and the product obtained in the downstream zone after the heat preservation is finished is the cerium-oxide-modified cobalt diselenide catalyst.
Preferably, the carbon cloth in step (1) is pretreated as follows before use: 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 according to 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 the 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, a step of; the concentration of urea was 1.67mol/L.
Preferably, the hydrothermal reaction in the step (1) is carried out for 6-12 hours.
Preferably, the soluble cobalt salt in the step (1) is at least one of cobalt sulfate, cobalt nitrate and cobalt acetate.
Preferably, the soluble cerium salt in the 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 selenium powder of step (3) is used in an amount of not less than 60% of the molar amount of the soluble cobalt salt of step (1).
Preferably, the reducing atmosphere in the step (3) is hydrogen.
The cerium oxide modified cobalt diselenide catalyst is prepared by the preparation method of the cerium oxide modified cobalt diselenide catalyst.
The application of the cerium oxide modified cobalt diselenide catalyst in preparing the electrocatalytic oxygen evolution material.
The reaction mechanism of the invention is as follows: the cobalt hydroxide and cerium hydroxide precursors which uniformly grow on the carbon cloth are obtained by utilizing a hydrothermal reaction, partial crystal water contained in the precursors is removed by high-temperature heat treatment in a protective atmosphere (which is beneficial to the selenizing reaction), cerium cobalt oxide is obtained, and finally, a target product is synthesized 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, wherein the catalyst has high catalytic activity, and the doping of cerium oxide enables the catalyst to expose more oxygen vacancy defects, accelerates the precipitation of oxygen and is beneficial to the occurrence of oxygen evolution reaction, so that the overpotential of the anode oxygen evolution reaction is reduced, the charge transfer kinetics of the electrode surface is accelerated, the catalytic reaction rate is accelerated, and the hydrogen production efficiency of the cobalt diselenide electrolysis water is further improved.
Drawings
FIG. 1 is an X-ray diffraction XRD pattern of a cerium oxide modified cobalt diselenide catalyst prepared in example 1.
Fig. 2 is a graph comparing oxygen evolution performance tests of the cerium oxide modified cobalt diselenide catalyst material prepared in example 1 and cobalt diselenide.
Fig. 3 is a graph comparing electrochemical impedance spectroscopy tests of the cerium oxide modified cobalt diselenide catalyst material prepared in example 1 and cobalt diselenide.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The carbon cloth described in the examples was purchased from CoTech technologies, model WOS 1009.
Example 1
A preparation method of a cerium oxide modified cobalt diselenide catalyst comprises the following steps:
(1) Firstly, pretreating carbon cloth: arranging carbon with the size of 1cm multiplied by 3cm in a tubular furnace, heating to 600 ℃ in air and preserving heat for 30min to remove a coating with non-hydrophilic surface, then carrying out ultrasonic treatment with deionized water for 30min, 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 for 6 hours at 120 ℃, growing to obtain cobalt hydroxide and cerium hydroxide on the carbon cloth, washing the carbon cloth coated with the cobalt hydroxide and the cerium hydroxide with deionized water and absolute ethyl alcohol for 2-3 times, and putting into a blast drying box at 60 ℃ for drying for standby;
(3) Disposing the cobalt hydroxide and cerium hydroxide coated carbon dried in the step (2) in a tube furnace for heat treatment, wherein the heat treatment parameters are set as follows: preserving heat for 3 hours at 300 ℃ and keeping the furnace atmosphere to be N 2 The flow rate was 50sccm. Obtaining cerium cobalt oxide after heat treatment;
(4) And (3) placing the cerium-cobalt oxide subjected to the heat treatment in the step (3) into a double-temperature-zone tube furnace for selenizing reaction for 1 hour. The reaction parameters were set as follows: placing 0.5g selenium powder in the upstream zone for 75 min, heating to 375 deg.C and maintaining for 1 hrThe method comprises the steps of carrying out a first treatment on the surface of the Placing cerium cobalt oxide in the downstream area, heating to 400 ℃ for 80 minutes, and preserving heat for 1 hour; the furnace atmosphere is H 2 The flow rate was 60sccm. After the reaction is finished, the substance prepared in the downstream area is the cerium oxide modified cobalt diselenide catalyst.
Selenium powder was excessive in this reaction, and it was evident that there was a residue after the reaction. And cobalt ions in the hydrothermal solution in the step (2) are not fully loaded on the carbon cloth.
X-ray diffraction XRD of the cerium oxide modified cobalt diselenide catalyst material prepared in example 1 is shown in FIG. 1. The synthetic material is in one-to-one correspondence with cerium oxide (PDF#34-0394) and cobalt diselenide (PDF#53-0449) through comparison with an XRD standard card database, 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 cerium oxide modified cobalt diselenide catalyst material prepared in example 1 and cobalt diselenide. Specific test conditions are based on a three-electrode electrochemical system, wherein an electrochemical workstation is a Shanghai Chen Huachi 660e electrochemical workstation, a reference electrode is a saturated calomel electrode, a counter electrode is a carbon rod, a working electrode is a catalyst sample fixed by a platinum clamp (the sample is cerium oxide modified cobalt diselenide catalyst material and pure cobalt diselenide prepared in example 1 respectively), the size of the sample is 0.6cm×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 5mV/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 cerium oxide modified cobalt diselenide catalyst is reduced by 160mV, which proves that the oxygen evolution reaction is easier to occur at the moment, and the cerium oxide doped catalyst has promotion effect on the catalytic reaction.
Fig. 3 is a graph comparing electrochemical impedance spectroscopy tests of the cerium oxide modified cobalt diselenide catalyst material and cobalt diselenide of example 1. Electrochemical Impedance Spectroscopy (EIS) is used to characterize electrode surface dynamics. The semicircle in the high frequency region represents the charge transfer process, the diameter of which is a resistance value, and is related to the charge transfer of the electrode interface, the smaller the charge transfer resistance, the faster the reaction rate. As can be seen from fig. 3: after cerium oxide is added for modification, the resistance value of the composite material is obviously reduced, which indicates that the charge transfer kinetics of the electrode material is accelerated and the catalytic reaction rate is accelerated. Specific test conditions were based on a three-electrode electrochemical system, the electrochemical workstation was a Shanghai Chen Huachi 660e electrochemical workstation, the reference electrode was a saturated calomel electrode, the counter electrode was a carbon rod, the working electrode was a catalyst sample fixed using a platinum clamp (the samples were the cerium oxide modified cobalt diselenide catalyst material and pure cobalt diselenide prepared in example 1, respectively), the sample size was 0.6cm×0.8cm, and the sample was placed in a 1.0M KOH electrolyte for electrochemical impedance testing. 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 carbon cloth: arranging carbon in a tubular furnace, heating to 650 ℃ in air and preserving heat for 20min to remove a coating with non-hydrophilic surface, then carrying out ultrasonic treatment with deionized water for 30min, and cleaning to remove 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 for 10 hours at 100 ℃, growing to obtain cobalt hydroxide and cerium hydroxide on the carbon cloth, washing the carbon cloth coated with the cobalt hydroxide and the cerium hydroxide with deionized water and absolute ethyl alcohol for 2-3 times, and putting into a blast drying box at 60 ℃ for drying for standby;
(3) Disposing the cobalt hydroxide and cerium hydroxide coated carbon dried in the step (2) in a tube furnace for heat treatment, wherein the heat treatment temperature parameter is set as follows: heat preservation at 450 ℃ for 1 hour, wherein the atmosphere condition in the furnace is N 2 The flow rate was 50sccm. Obtaining cerium cobalt oxide after heat treatment;
(4) And (3) placing the cerium-cobalt oxide subjected to the heat treatment in the step (3) into a double-temperature-zone tube furnace for selenizing reaction for 2 hours. The reaction parameters were set as follows: placing 0.5g of selenium powder in the upstream area, heating to 300 ℃ for 55 minutes, and preserving heat for 2 hours; downstream zone placement of cerium cobalt oxideThe temperature was raised to 300℃over 60 minutes and kept at that temperature for 2 hours. The furnace atmosphere is H 2 The flow rate was 60sccm. After the reaction is finished, the substance prepared in the downstream area 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 carbon cloth: arranging carbon in a tubular furnace, heating to 700 ℃ in air and preserving heat for 10min to remove a coating with non-hydrophilic surface, then carrying out ultrasonic treatment with deionized water for 30min, 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 for 4 hours at 180 ℃, growing to obtain cobalt hydroxide and cerium hydroxide on the carbon cloth, washing the carbon cloth coated with the cobalt hydroxide and the cerium hydroxide with deionized water and absolute ethyl alcohol for 2-3 times, and putting into a blast drying box at 60 ℃ for drying for standby;
(3) Disposing the cobalt hydroxide and cerium hydroxide coated carbon dried in the step (2) in a tube furnace for heat treatment, wherein the heat treatment temperature parameter is set as follows: preserving heat for 2 hours at 400 ℃ and keeping the atmosphere condition in the furnace as N 2 The flow rate was 50sccm. Obtaining cerium cobalt oxide after heat treatment;
(4) And (3) arranging the cerium cobalt oxide carbon subjected to the heat treatment in the step (3) in a double-temperature-zone tube furnace for selenizing reaction for 1h. The reaction parameters were set as follows: placing 0.5g of selenium powder in the upstream area, heating to 500 ℃ for 95 minutes, and preserving heat for 1 hour; the downstream zone was placed with cerium cobalt oxide and warmed to 500 ℃ for 100 minutes and incubated for 1 hour. The furnace atmosphere is H 2 The flow rate was 60sccm. After the reaction is finished, the substance prepared in the downstream area is the cerium oxide modified cobalt diselenide catalyst.
Oxygen evolution performance and electrochemical impedance spectroscopy of the cerium oxide modified cobalt diselenide catalysts prepared in examples 2 and 3 were similar to example 1.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (6)
1. The application of the cerium oxide modified cobalt diselenide catalyst in preparing the electrocatalytic oxygen evolution material is characterized in that the preparation method of the cerium oxide modified cobalt diselenide catalyst comprises the following steps:
(1) Placing carbon cloth in a mixed solution of soluble cobalt salt and soluble cerium salt, and performing hydrothermal reaction at 100-180 ℃ to obtain cobalt hydroxide and cerium hydroxide coated carbon cloth;
the mixed solution in the step (1) is prepared according to 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 the 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, a step of; the concentration of the urea is 1.67 mol/L;
(2) The cobalt hydroxide and the carbon cloth coated by the cerium hydroxide in the step (1) are subjected to heat preservation for 1-3 hours at 300-450 ℃ under the protective atmosphere, so as to obtain cerium cobalt oxide;
(3) Placing the cerium-cobalt oxide and the selenium powder obtained in the step (2) into a double-temperature-zone tube furnace and preserving heat for 1-2 hours in a reducing atmosphere, wherein the selenium powder is positioned in an upstream zone of 300-375 ℃, the cerium-cobalt oxide is positioned in a downstream zone of 300-500 ℃, and a product obtained in the downstream zone after the heat preservation is finished is the cerium-oxide-modified cobalt diselenide catalyst;
the selenium powder in the step (3) is used in an amount of not less than 60% of the molar amount of the soluble cobalt salt in the step (1).
2. The use of a cerium oxide modified cobalt diselenide catalyst according to claim 1 for the preparation of an electrocatalytic oxygen evolution material, wherein the carbon cloth of step (1) is pre-treated prior to 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.
3. The application of the cerium oxide modified cobalt diselenide catalyst in preparing the electrocatalytic oxygen evolution material according to claim 2, wherein the hydrothermal reaction time in the step (1) is 6-12 h.
4. The use of a cerium oxide modified cobalt diselenide catalyst according to claim 1, wherein the soluble cobalt salt of step (1) is at least one of cobalt sulfate, cobalt nitrate and cobalt acetate.
5. The use of a cerium oxide modified cobalt diselenide catalyst according to claim 4, wherein said soluble cerium salt of step (1) is at least one of cerium nitrate, ammonium cerium sulfate hydrate and cerium sulfate.
6. The use of a cerium oxide modified cobalt diselenide catalyst in the preparation of an electrocatalytic oxygen evolution material as set forth in claim 1, wherein the protective atmosphere of step (2) is N 2 And Ar;
the reducing atmosphere in the step (3) is hydrogen.
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