CN111330622B - Preparation method of nitrogen-doped heterogeneous catalyst for oxygen production by electrolyzing water - Google Patents
Preparation method of nitrogen-doped heterogeneous catalyst for oxygen production by electrolyzing water Download PDFInfo
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- 239000001301 oxygen Substances 0.000 title claims abstract description 33
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- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 10
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 10
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- 238000006243 chemical reaction Methods 0.000 claims description 23
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- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
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- 238000011161 development Methods 0.000 description 5
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- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
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- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/61—
-
- 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
-
- 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 preparation method of a nitrogen-doped heterogeneous catalyst for oxygen production by electrolyzing water, which comprises the following steps: dissolving cobalt acetate, thiourea and ammonium fluoride in a mixed solvent consisting of deionized water and ethylene glycol to obtain a precursor solution, transferring the precursor solution into a hydrothermal kettle, adding foamed nickel, carrying out solvothermal one-pot reaction, and carrying out twice temperature rise to grow Co of a heterostructure on the foamed nickel in situ Co-production manner4S3/Ni3S2After the solvothermal reaction of the nano-sheet composite material is finished, the foamed nickel-based composite material is subjected to high-temperature nitridation treatment, and finally the foamed nickel-based nitrogen-doped oxygen production heterogeneous catalyst by water electrolysis is obtained. The invention adopts the nano-sheet composite material which grows on the foam nickel in situ as the catalyst for preparing oxygen by electrolyzing water, reduces the cost of the catalyst compared with the catalyst for preparing oxygen by electrolyzing water by noble metal and oxide thereof, and improves the intrinsic catalytic activity of the catalyst for preparing oxygen by electrolyzing water compared with the transition metal sulfide nano-sheet catalyst which has single component and is not doped and modified.
Description
Technical Field
The invention relates to a preparation method of a nitrogen-doped heterogeneous catalyst for oxygen production by electrolyzing water, belonging to the field of energy and catalytic materials.
Technical Field
The sustainable development of human society faces many challenges such as the problem of environmental pollution caused by the limited reserves of fossil fuels, and the preparation of hydrogen and oxygen by electrolyzing water is a method for preparing clean energy on a large scale with great development prospect. However, the higher kinetic barrier of the water electrolysis oxygen production faces, the efficiency of water decomposition is limited, and therefore, the development of an efficient and cheap water electrolysis oxygen production catalyst is crucial. At present, noble metal oxides such as iridium dioxide and ruthenium dioxide are considered to be the most efficient catalysts for the oxygen production by water electrolysis, but the scarcity and high cost limit the large-scale application of the catalysts for the oxygen production by water electrolysis. Therefore, the development of cheap, stable and efficient catalyst for oxygen production by water electrolysis is an important problem to be solved urgently in the economic development of hydrogen. The transition metal has relatively low price, and the sulfide thereof has good electrocatalytic activity and is concerned by extensive researchers.
At present, transition metal compounds as electrocatalytic oxygen evolution catalysts generally need to be loaded on other conductive substrates by using adhesives for convenient application, but the combination mode of the catalysts and the substrates is not firm, and seriously hinders charge transmission, and the full exposure of active sites of the catalysts is limited, so that the activity and the catalytic efficiency of the catalysts are reduced, and the waste of materials and energy is caused.
Disclosure of Invention
The invention aims to provide a method for preparing a nitrogen-doped oxygen production heterogeneous catalyst by electrolyzing water, which is based on solvothermal one-pot reaction, realizes the in-situ co-growth of a heterostructure nanosheet by adjusting the temperature of different stages of the solvothermal reaction, and manufactures a large number of lattice defects as electrocatalytic active sites.
Specifically, by adjusting the reaction temperature and the reaction time, in the first stage of the solvothermal one-pot reaction, the material characteristics that the solubility product constant of cobalt hydroxide is greater than that of nickel hydroxide and the solubility product constant of cobalt sulfide is less than that of nickel sulfide are utilized, and under the help of a certain proportion of ammonium fluoride, a large amount of nickel ions escape from the surface of the foamed nickel, the concentration of the nickel ions in the mixed solution is rapidly increased, and the cobalt hydroxide is ensured not to be preferentially crystallized; in the second stage of solvothermal one-pot reaction, Co is in the solution environment on the surface of the foamed nickel under the action of thiourea in a certain proportion4S3And Ni3S2Co with crystal Co-grown into heterostructure4S3/Ni3S2Nanosheets, and Co with the aid of a proportion of ethylene glycol coordinated metal ions4S3The nano-crystal can be uniformly embedded in Ni3S2Nanosheet, finally realizing in-situ Co-growth of heterostructure Co on the surface of foamed nickel4S3/Ni3S2The preparation method of the nano-sheet is simple and effective.
Specifically, nitrogen atoms are doped into Co in situ symbiosis by adjusting nitriding temperature and nitriding time4S3/Ni3S2In nano-scale, based on Co4S3/Ni3S2In the heterostructure nanosheets, Co4S3Nanocrystalline and Ni3S2The joints between the nano sheets have a large number of lattice defects and nitrogen atoms are moreEasily concentrated in Co4S3Nanocrystalline and Ni3S2At the joint between the nano sheets, Ni with stable structure is finally obtainedxCo1-xSyN1-yNanosheets.
The invention also aims to provide a method for preparing the nitrogen-doped water electrolysis oxygen production heterogeneous catalyst, which realizes nitrogen atom doping based on high-temperature nitridation reaction so as to adjust the electronic structure of metal sulfide and further improve the intrinsic catalytic activity of the water electrolysis oxygen production catalyst with the heterostructure nanosheets.
The invention also aims to provide a method for preparing the nitrogen-doped oxygen production heterogeneous catalyst by electrolyzing water, which adopts three-dimensional macroporous foam nickel as a framework load heterogeneous structure nanosheet, and the multilevel structure has large specific surface area, is favorable for mass transfer and oxygen precipitation and is more favorable for fully exposing an electrocatalytic active site.
The technical scheme of the invention is as follows: a preparation method of a nitrogen-doped oxygen production heterogeneous catalyst by electrolyzing water comprises the following steps: dissolving cobalt acetate, thiourea and ammonium fluoride in a mixed solvent consisting of deionized water and ethylene glycol to obtain a precursor solution, transferring the precursor solution into a hydrothermal kettle, adding foamed nickel, and carrying out a solvothermal one-pot reaction comprising two stages, wherein the temperature of the first stage is 120 ℃, the heat preservation time is 4 hours, the temperature of the second stage is 160 ℃, the heat preservation time is 3 hours, and after the reaction is finished, naturally cooling, taking out a product, washing and drying to obtain a foamed nickel-based composite material; then carrying out high-temperature nitridation reaction to realize nitrogen atom doping, specifically: performing nitridation reaction under an ammonia environment by taking ammonia as a nitrogen source, wherein the temperature of the nitridation reaction is 300 ℃, the nitridation time is 40min, and the heating rate is 10 ℃/min; finally obtaining the foam nickel-based nitrogen-doped water electrolysis oxygen production heterogeneous catalyst.
Further, when the precursor solution is prepared, the mass ratio of the cobalt acetate, the thiourea and the ammonium fluoride is 3:15:1, and the volume ratio of the deionized water and the ethylene glycol is 1: 2. The feed-liquid ratio of the total mass of the cobalt acetate, the thiourea and the ammonium fluoride to the total volume of the deionized water and the ethylene glycol is 190 g/21L.
Further, the size of the added nickel foam is 1X 4cm2。
The invention has the beneficial effects that: co is added by adjusting the time, temperature and drug dosage of the solvothermal one-pot reaction4S3The nano-crystal is uniformly embedded in Ni3S2Co of nanosheets4S3/Ni3S2Nano-sheets are uniformly Co-grown on the foamed nickel in situ, and the stable structure and the nitrogen atoms enriched in Co are further obtained through a high-temperature nitridation reaction4S3Nanocrystalline and Ni3S2Ni at the junction between nanosheetsxCo1-xSyN1-yNano-sheet to obtain high-efficiency foam nickel-based NixCo1-xSyN1-yThe catalyst is prepared by electrolyzing water with a nano-sheet composite material.
Drawings
FIG. 1 shows Ni-foam nickel prepared in example 1xCo1-xSyN1-yOxygen generation electrocatalyst made of nanosheet composite material and foam nickel-based nitrogen-doped Ni prepared in comparative example 13S2An X-ray diffraction pattern of the oxygen-generating electrocatalyst made of the nano-sheet composite material;
in FIG. 2, (a) shows Ni based on the foamed nickel obtained in example 1xCo1-xSyN1-yAn integral scanning electron microscope image of the oxygen-generating electrocatalyst made of the nano-sheet composite material; (b) for the foamed nickel base obtained in example 1, nitrogen-doped Co4S3/Ni3S2Scanning pictures of the nanosheet composite material electrolyzed water to prepare the oxygen electrocatalyst under a higher magnification factor;
in FIG. 3, (a) shows Ni based on the foamed nickel obtained in example 1xCo1-xSyN1-yA high-resolution transmission electron microscope image of the oxygen-generating electrocatalyst made of the nano-sheet composite material; (b) foamed nickel-based Ni obtained for example 1xCo1-xSyN1-yA high-resolution transmission electron microscope image of the nano-sheet composite material electrolyzed water oxygen-making electrocatalyst under higher magnification;
FIG. 4 shows Ni foam nickel base obtained in example 1xCo1-xSyN1-yElectrochemical performance diagram of oxygen generation electrocatalyst made of nano-sheet composite material: linear sweep voltammetry curve (a), tafel slope curve (b), and overpotential histogram (c).
Detailed Description
The present invention will be specifically described or further illustrated below with reference to examples, which are intended to better understand the technical spirit of the present invention, but the scope of the present invention is not limited to the following embodiments.
Example 1:
solvothermal one-pot reaction: 30mg of cobalt acetate, 150mg of thiourea and 10mg of ammonium fluoride were dissolved in a mixed solvent of 7mL of deionized water and 14mL of ethylene glycol, and the solution was charged into a high-temperature high-pressure reaction vessel of 100m L, and simultaneously, 1X 4cm of the solution was washed and placed in the vessel2Foaming nickel, then placing the high-temperature high-pressure reaction kettle into a constant-temperature oven at 120 ℃, preserving heat for 4 hours, then heating to 160 ℃, preserving heat for 3 hours, naturally cooling, taking out, washing and drying to obtain the foam nickel-based Co4S3/Ni3S2A nanosheet composite.
High-temperature nitriding reaction: taking ammonia gas as nitrogen source, before the start of the nitridation reaction, nickel foam base Co4S3/Ni3S2Placing the nano-sheet composite material in a quartz boat, placing the quartz boat in a quartz tube in a tube type resistance furnace, sealing the quartz tube, fully vacuumizing, and then filling ammonia gas until the air pressure is 0; heating to 300 ℃ at a speed of 10 ℃/min, keeping the temperature for 40min, and then naturally cooling to obtain the foam nickel-based NixCo1-xSyN1-yNanosheet composite, numbered NixCo1-xSyN1-y/NF。
Comparative example 1:
the difference from example 1 is that: cobalt acetate is not added in the solvothermal one-pot reaction, and the rest is the same as the example 1, so that the foam nickel-based nitrogen-doped Ni is obtained3S2Nanosheet composite, numbered Ni3SmN2-m/NF。
Catalyst structural characterization
FIG. 1 shows preparation of example 1Catalyst NixCo1-xSyN1-yCatalyst Ni prepared by/NF and comparative example 13SmN2-mX-ray diffraction analysis pattern of/NF. As can be seen from fig. 1: ni was observed in the catalysts prepared in example 1 and comparative example 13S2Diffraction peaks corresponding to characteristic peaks of metallic nickel at 21.7 °, 31.1 °, 37.8 °, 49.7 °, 50.2 °, 55.1 °, 55.3 °, 69.3 °, 73.0 ° and 77.9 ° respectively correspond to Ni3S2The (101), (110), (003), (113), (211), (122), (300), (131), (214) and (401) crystal planes of (JCPDS No.44-1418) are marked with solid diamond symbols, and the diffraction peaks at 44.5 degrees, 51.8 degrees and 76.4 degrees correspond to the elemental Ni in the base nickel foam (JCPDS No.04-0850) and are marked with open to triangular symbols. The catalyst prepared in example 1 showed significantly more Co than the catalyst prepared in comparative example 1 in composition4S3The diffraction peaks at 30.0 ° and 50.0 ° respectively correspond to Co4S3(JCPDS No.30-0458) (111) and (220) and the crystal planes, marked with solid circle symbols in the figure. In addition, no other miscellaneous peaks appear in the figure, showing higher purity.
FIG. 2 shows Ni catalyst prepared in example 1xCo1-xSyN1-yScanning electron micrographs of/NF (a, b at different magnifications). 2a the macroporous nickel foam skeleton can be observed, and Co4S3/Ni3S2The nano-sheet grows on the macroporous foam nickel framework in situ. 2b it can be observed that Co grows uniformly and vertically on the surface of the nickel foam4S3/Ni3S2The structure of the nano-sheet provides a wide space for mass transfer and oxygen evolution. After high-temperature nitridation, the macroporous foam nickel skeleton and the vertical nanosheets still keep complete, which indicates that the composite material has good mechanical stability.
FIG. 3 shows Ni catalyst prepared in example 1xCo1-xSyN1-yHigh resolution transmission electron micrographs of/NF (a, b at different magnifications). 3a, it was observed that spots of relatively higher contrast were uniformly embedded on the nanosheets. 3b, lattice striations were observed, while those observed in the higher contrast dotsIn Co4S3The (111) and (220) crystal planes of (A) and (B) in which a portion with low contrast is observed to belong to Ni3S2The (110) and (202) crystal planes of (a). Demonstration of Co4S3The nano-crystal is uniformly embedded in Ni3S2Co Co-forming heterostructures on nano-sheets4S3/Ni3S2Nanosheets.
FIG. 4 shows NixCo1-xSyN1-yThe electrolytic water performance curve diagram of the/NF composite material is respectively a linear scanning voltammetry curve (a), a tafel slope curve (b) and an overpotential histogram (c).
Testing of catalyst Performance
Catalyst Ni prepared in example 1xCo1-xSyN1-yCatalyst Ni prepared by/NF and comparative example 13SmN2-mand/NF is used for the performance test of the water electrolysis oxygen generation experiment.
A three-electrode system is adopted to test a linear sweep voltammetry curve, a Tafel slope curve, an electrochemical impedance spectrum Nyquist curve and an overpotential histogram, and the three-electrode system is divided into a working electrode, a reference electrode and a counter electrode. The reference electrode is an Ag/AgCl electrode, the counter electrode is a carbon rod, the working electrode is the catalyst material, and the platinum sheet electrode clamp is used for clamping the catalyst and then directly used as the working electrode.
The above experiments were all performed in 1.0M KOH solution, where the test conditions were: the linear scanning sweep rate is 1mV s-1The tafel slope curve is fitted by a linear sweep voltammetric curve.
FIG. 4 shows NixCo1-xSyN1-yThe electrolytic water performance curve diagram of the/NF composite material is respectively a linear scanning voltammetry curve (a), a tafel slope curve (b) and an overpotential histogram (c). As is evident from fig. 4: nixCo1-xSyN1-ythe/NF composite material is at 20mA cm-2The overpotential is 176mV much less than Ni3SmN2-m/NF Material at 20mA cm-2The catalyst is overpotential, and shows higher catalytic performance;NixCo1-xSyN1-ythe Tafel slope of the/NF composite material is 118mV decade-1Far less than Ni3SmN2-mTafel slope of/NF material. The reason is that the preparation method of the composite material of the foam nickel self-growing nano-sheet is beneficial to improving the electron transfer rate in the electrocatalysis process; a large number of lattice defects are manufactured as electrocatalytic active sites by a construction method of symbiotically growing heterostructure nanosheets by adjusting temperatures at different stages of solvothermal reaction; the intrinsic catalytic activity of the catalyst for preparing oxygen by electrolyzing water with the heterostructure nanosheet is further improved by doping nitrogen atoms to adjust the electronic structure of the metal sulfide; the specific surface area of the three-dimensional macroporous foam nickel framework loaded with the heterostructure nanosheets is large and stable, and full exposure of electrocatalytic active sites, mass transfer and oxygen precipitation are facilitated. The solvent thermal one-pot reaction is used for preparing foam nickel-based NixCo1-xSyN1-yThe preparation method of the nano-sheet composite material integrates the combined action of various modification means, and effectively improves the foam nickel-based NixCo1-xSyN1-yThe intrinsic catalytic activity and the water electrolysis oxygen generation efficiency of the nanosheet composite material water electrolysis oxygen generation catalyst are improved.
Comparative example 2:
solvothermal one-pot reaction: 30mg of cobalt acetate, 150mg of thiourea and 10mg of ammonium fluoride were dissolved in a mixed solvent of 7mL of deionized water and 14mL of ethylene glycol, and the solution was charged into a high-temperature high-pressure reaction vessel of 100m L, and simultaneously, 1X 4cm of the solution was washed and placed in the vessel2Foaming nickel, then placing the high-temperature high-pressure reaction kettle into a constant-temperature oven at 120 ℃, preserving heat for 2 hours, then heating to 160 ℃, preserving heat for 1 hour, naturally cooling, taking out, washing and drying to obtain the foam nickel-based Co4S3/Ni3S2A nanosheet composite.
High-temperature nitriding reaction: taking ammonia gas as nitrogen source, before the start of the nitridation reaction, nickel foam base Co4S3/Ni3S2Placing the nano-sheet composite material in a quartz boat, placing the quartz boat in a quartz tube in a tube-type resistance furnace, sealing the quartz tube, fully vacuumizing, and introducing ammonia gas to the quartz tubeThe pressure is 0; heating to 200 ℃ at a speed of 10 ℃/min, keeping the temperature for 30min, and then naturally cooling to obtain the foam nickel-based NixCo1-xSyN1-yNano sheet composite material numbered 3h-NixCo1-xSyN1-y/NF。
3h-Ni prepared in comparative example 2 was analyzed for catalytic performance with reference to example 1xCo1-xSyN1-ythe/NF composite material is at 20mA cm-2The overpotential is 255mV and more than NixCo1-xSyN1-y/NF Material at 20mA cm-2The catalyst is overpotential, and shows poor catalytic performance; 3h-NixCo1-xSyN1-yThe Tafel slope of the/NF composite material is 132mV decade-1Is greater than NixCo1-xSyN1-yTafel slope of/NF material. Illustrating that the use of shorter reaction times is not conducive to the formation of heterostructured nanosheet composites with good crystallinity with high catalytic performance.
Comparative example 3:
solvothermal one-pot reaction: 30mg of cobalt acetate, 150mg of thiourea and 10mg of ammonium fluoride were dissolved in a mixed solvent of 7mL of deionized water and 14mL of ethylene glycol, and the solution was charged into a high-temperature high-pressure reaction vessel of 100m L, and simultaneously, 1X 4cm of the solution was washed and placed in the vessel2Foaming nickel, then placing the high-temperature high-pressure reaction kettle into a constant-temperature oven at 120 ℃, preserving heat for 8 hours, then heating to 160 ℃, preserving heat for 9 hours, naturally cooling, taking out, washing and drying to obtain the foam nickel-based Co4S3/Ni3S2A nanosheet composite.
High-temperature nitriding reaction: taking ammonia gas as nitrogen source, before the start of the nitridation reaction, nickel foam base Co4S3/Ni3S2Placing the nano-sheet composite material in a quartz boat, placing the quartz boat in a quartz tube in a tube type resistance furnace, sealing the quartz tube, fully vacuumizing, and then filling ammonia gas until the air pressure is 0; heating to 400 ℃ at the speed of 10 ℃/min, keeping the temperature for 40min, and then naturally cooling to obtain the foam nickel-based NixCo1-xSyN1-yA nano-sheet composite material with the serial number of 17h-NixCo1-xSyN1-y/NF。
Reference example 1 was conducted to analyze catalytic performance, 17h-Ni prepared in this comparative example 3xCo1-xSyN1-ythe/NF composite material is at 20mA cm-2The overpotential is 327mV higher than NixCo1-xSyN1-y/NF Material at 20mA cm-2The catalyst is overpotential, and shows poor catalytic performance; 17h-NixCo1-xSyN1-yThe Tafel slope of the/NF composite material is 137mV decade-1Is greater than NixCo1-xSyN1-yTafel slope of/NF material. It is shown that the use of longer reaction times rather reduces the catalytic performance of the composite, probably because the heteronanosheet structure is destroyed at elevated temperatures for too long a period of time.
Claims (2)
1. A preparation method of a nitrogen-doped oxygen production heterogeneous catalyst by electrolyzing water is characterized by comprising the following steps:
dissolving cobalt acetate, thiourea and ammonium fluoride in a mixed solvent consisting of deionized water and ethylene glycol to obtain a precursor solution, transferring the precursor solution into a hydrothermal kettle, adding foamed nickel, and carrying out a solvothermal one-pot reaction containing two stages;
wherein the temperature of the first stage is 120 ℃, the heat preservation time is 4 hours, the temperature of the second stage is 160 ℃, the heat preservation time is 3 hours, after the reaction is finished, the reaction product is naturally cooled, and the product is taken out, washed and dried to obtain the foam nickel-based composite material;
then, carrying out high-temperature nitridation reaction to realize nitrogen atom doping, specifically: performing nitridation reaction under an ammonia environment by taking ammonia as a nitrogen source, wherein the temperature of the nitridation reaction is 300 ℃, the nitridation time is 40min, and the heating rate is 10 ℃/min;
finally obtaining the foam nickel-based nitrogen-doped water electrolysis oxygen production heterogeneous catalyst;
when the precursor solution is prepared, the mass ratio of the cobalt acetate, the thiourea and the ammonium fluoride is 3:15:1, and the volume ratio of the deionized water and the ethylene glycol is 1: 2.
2. The method of claim 1, wherein the added nickel foam has a size of 1 x 4cm2。
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