CN113457680B - Cobalt catalyst and preparation method thereof - Google Patents
Cobalt catalyst and preparation method thereof Download PDFInfo
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- CN113457680B CN113457680B CN202010242556.7A CN202010242556A CN113457680B CN 113457680 B CN113457680 B CN 113457680B CN 202010242556 A CN202010242556 A CN 202010242556A CN 113457680 B CN113457680 B CN 113457680B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 80
- 239000010941 cobalt Substances 0.000 title claims abstract description 80
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002077 nanosphere Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 29
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 239000013543 active substance Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 31
- -1 cobalt oxyhydroxide Chemical group 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 30
- 239000003792 electrolyte Substances 0.000 claims description 24
- 239000006260 foam Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 19
- 230000001681 protective effect Effects 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 239000011593 sulfur Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 230000003213 activating effect Effects 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 12
- 238000002484 cyclic voltammetry Methods 0.000 claims description 11
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 6
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- 239000011149 active material Substances 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000004832 voltammetry Methods 0.000 claims description 4
- 238000004769 chrono-potentiometry Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 5
- 239000002135 nanosheet Substances 0.000 abstract description 4
- 239000000843 powder Substances 0.000 description 32
- 239000007789 gas Substances 0.000 description 31
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000010431 corundum Substances 0.000 description 19
- 229910052593 corundum Inorganic materials 0.000 description 19
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 229910002804 graphite Inorganic materials 0.000 description 13
- 239000010439 graphite Substances 0.000 description 13
- 229910052786 argon Inorganic materials 0.000 description 12
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 12
- 229910052753 mercury Inorganic materials 0.000 description 12
- 229910000474 mercury oxide Inorganic materials 0.000 description 12
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- DSLRVRBSNLHVBH-UHFFFAOYSA-N HMF alcohol Natural products OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- NSQYDLCQAQCMGE-UHFFFAOYSA-N 2-butyl-4-hydroxy-5-methylfuran-3-one Chemical compound CCCCC1OC(C)=C(O)C1=O NSQYDLCQAQCMGE-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- NSRBDSZKIKAZHT-UHFFFAOYSA-N tellurium zinc Chemical compound [Zn].[Te] NSRBDSZKIKAZHT-UHFFFAOYSA-N 0.000 description 7
- 238000004506 ultrasonic cleaning Methods 0.000 description 5
- PCSKKIUURRTAEM-UHFFFAOYSA-N 5-hydroxymethyl-2-furoic acid Chemical compound OCC1=CC=C(C(O)=O)O1 PCSKKIUURRTAEM-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
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- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000004098 selected area electron diffraction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
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- 238000004073 vulcanization Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241001092080 Hydrangea Species 0.000 description 2
- 235000014486 Hydrangea macrophylla Nutrition 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- SSXJHQZOHUYEGD-UHFFFAOYSA-N 3,3',4',5,6,7,8-Heptamethoxyflavone Natural products C1=C(OC)C(OC)=CC=C1C1=C(OC)C(=O)C2=C(OC)C(OC)=C(OC)C(OC)=C2O1 SSXJHQZOHUYEGD-UHFFFAOYSA-N 0.000 description 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- DLVYTANECMRFGX-UHFFFAOYSA-N norfuraneol Natural products CC1=C(O)C(=O)CO1 DLVYTANECMRFGX-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
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Images
Classifications
-
- B01J35/51—
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/33—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- 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
-
- 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 cobalt catalyst and a preparation method thereof, wherein the cobalt catalyst comprises a carrier and a catalytic active substance; the carrier is a cobalt-based substrate material; the catalytic active substance grows on the surface of the carrier; the shape of the catalytic active substance is a hydrangea-shaped nanosphere. The catalyst is an integral nanosphere catalyst which grows automatically, the surface of the catalyst is of a three-dimensional structure formed by assembling nanosheets, the specific surface area is high, catalytic active sites can be fully exposed, and the catalytic efficiency is improved. Compared with the nanometer linear catalyst, the catalyst has better self-supporting property, the active components are not easy to aggregate and fall off in the application process, and the service life is longer.
Description
Technical Field
The invention belongs to the technical field of chemical catalysis, and particularly relates to a cobalt catalyst and a preparation method thereof.
Background
The noble metal has excellent catalytic performance and is a star in the field of catalysis. However, the availability of precious metals such as palladium, platinum, gold, ruthenium, iridium and the like is limited and expensive, so that commercial catalysis using precious metals on a large scale is not a long standing proposition. In the face of the above problems, attention has been focused on the development and utilization of transition metals having various valence states.
Cobalt is one of transition metals, has certain catalytic performance, and is rich in reserves and low in price compared with noble metals. Most of the cobalt-based catalysts are oxides, sulfides, borides and the like of cobalt, and the catalytic capability of the cobalt-based catalysts can be compared with that of noble metals in certain reactions.
The cobalt-based catalyst is usually a supported catalyst, and the falling and loss of active components are easy to occur in the using process, so that the catalyst is gradually deactivated, the product is difficult to separate and purify, and the operation steps and the production cost of the whole catalytic reaction process are increased.
Disclosure of Invention
In order to solve the technical problems, the invention provides a cobalt catalyst and a preparation method thereof, wherein a catalytic active substance is grown on the surface of a cobalt-based substrate material, so that the binding force of the active substance on a carrier is improved, the service life of the catalyst can be prolonged, and the loss of active components can be reduced.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in one aspect of the present invention, a cobalt catalyst is provided, the cobalt catalyst comprising a carrier and a catalytically active material;
the carrier is a cobalt-based substrate material;
the catalytic active substance grows on the surface of the carrier;
the appearance of the catalytic active substance is hydrangea-shaped nanospheres.
Optionally, the catalytically active material is grown on the surface of the carrier by using the carrier as a cobalt source and self-source.
Optionally, the cobalt-based substrate material is selected from at least one of cobalt foam, cobalt flakes, cobalt foil, cobalt filament.
Optionally, the nanospheres have a diameter of 100 to 500nm.
Optionally, the thickness of the nanosphere surface sheet layer is 1-10 nm.
Optionally, the catalytically active material is cobalt oxyhydroxide.
In another aspect of the present invention, a method for preparing a cobalt catalyst is provided, the method at least comprising:
s100, heating and reacting the carrier and a sulfur source in a protective gas atmosphere to obtain a precursor;
and S200, electro-activating the precursor in electrolyte to obtain the cobalt catalyst.
Optionally, step S100 is:
a. obtaining a dry powder as a sulfur source;
b. immersing the carrier in washing liquid, washing and drying;
c. and heating and reacting the dried powder and the carrier in the atmosphere of protective gas to obtain the precursor.
Specifically, the step a is as follows: drying the sulfur source at a certain temperature for a certain time in the atmosphere of protective gas with a certain flow rate.
Wherein the certain temperature is 20-40 ℃;
the protective gas is at least one of nitrogen, argon and helium;
the flow of the protective gas is as follows: 50 mL/min-150 mL/min;
preferably, the sulfur source is dried at 30 ℃ for a certain time in a nitrogen atmosphere of 100mL/min to remove the contained water.
In the present application, the drying time of the sulfur source selected is not particularly limited. In order to prepare the integral hydrangea-shaped cobalt oxyhydroxide nanosphere catalyst with excellent performance and ensure the purity of the product, the drying time is preferably 1-5 h.
Specifically, in the step b, the washing solution is at least one selected from absolute ethyl alcohol and acetone;
the washing mode is as follows: ultrasonic cleaning is carried out for 5-30 min;
the drying conditions were: drying for 2-6 h at 40-60 ℃.
Preferably, step b is: the carrier was immersed in absolute ethanol and ultrasonically cleaned for 10min, and then dried at 60 ℃ for 4h.
In order to successfully prepare the monolithic catalyst, the carrier should be a cobalt-based material, and preferably, the carrier such as cobalt foam, cobalt sheet, cobalt foil and the like which has self-supporting properties meets the requirements.
Specifically, step S100 employs a heating furnace as the reaction apparatus. In the step, the precursor is obtained through a vulcanization process, wherein the heating furnace is preferably a tubular furnace with a built-in quartz tube or corundum tube for facilitating the introduction of protective gas, and the protective gas is preferably one or more of nitrogen, argon and helium. The flow rate of the shielding gas is not excessively large, and the flow rate is preferably 10mL/min to 100mL/min. Under the flow, dry sulfur source powder can be prevented from being blown away directly, ablation of products can be prevented, the quality of the products is improved, and the mechanical property and the chemical property of the products are further enhanced.
Specifically, the upper flow limit of the protective gas is independently selected from 60mL/min, 70mL/min, 80mL/min, 90mL/min and 100mL/min; the lower flow limit of the protective gas is independently selected from 10mL/min, 20mL/min, 30mL/min, 40mL/min, and 50mL/min.
Optionally, in step S100, the mass ratio of the sulfur source to the carrier is 2 to 10;
preferably, the sulfur source is at least one of sublimed sulfur, sodium sulfide and thiourea.
Specifically, the upper limit of the mass ratio of the sulfur source to the carrier is independently selected from 4:1, 5:1, 7:1, 8:1, 10; the lower limit of the mass ratio of the sulfur source to the carrier is independently selected from 2:1, 3:1, 3.8.
Optionally, in step S100, the temperature of the heating reaction is 300 ℃ to 400 ℃, and the reaction time is 0.25h to 2h;
in order to ensure the quality of the product, the heating speed is not too fast, and preferably, the heating rate of the heating reaction is 5-10 ℃/min.
Specifically, the upper limit of the heating reaction temperature is independently selected from 350 ℃, 360 ℃, 370 ℃, 380 ℃ and 400 ℃; the lower limit of the heating reaction temperature is independently selected from 300 deg.C, 310 deg.C, 320 deg.C, 330 deg.C, and 340 deg.C.
Specifically, the upper limit of the reaction time is independently selected from 1h, 1.2h, 1.5h, 1.7h, 2h; the lower limit of the reaction time is independently selected from 0.25h, 0.5h, 0.75h, 1h, 1.25h.
Specifically, the upper limit of the heating rate is independently selected from 7.5 ℃/min, 8 ℃/min, 8.5 ℃/min, 9 ℃/min and 10 ℃/min; the lower limit of the heating rate is independently selected from 5 ℃/min, 5.5 ℃/min, 6 ℃/min, 6.5 ℃/min and 7 ℃/min.
Optionally, step S200 is:
and taking the precursor as an anode, and performing electric activation, washing and drying in electrolyte to obtain the cobalt catalyst.
Specifically, the precursor can be used as an anode, and then assembled with a cathode and a reference electrode to form a three-electrode electrolytic cell, and the three-electrode electrolytic cell is electrically activated in an electrolyte, washed and dried to obtain the cobalt catalyst.
Optionally, the cathode is: at least one of a graphite rod, a platinum wire, a platinum net and a platinum sheet;
the reference electrode is: any one of a mercury/mercury oxide electrode, a saturated calomel electrode and a silver/silver chloride electrode;
the electrolyte is at least one of potassium hydroxide solution and sodium hydroxide solution;
the concentration of the electrolyte is 0.01M-1M.
Preferably, step S200 is: and (3) taking the precursor as an anode, taking a graphite rod as a cathode, taking a mercury/mercury oxide electrode as a reference electrode, assembling the three electrodes into a three-electrode electrolytic cell together, performing electric activation in an electrolyte with the concentration of 1M, washing and drying to obtain the integral hydrangea-shaped cobalt oxyhydroxide nanosphere catalyst.
Specifically, the upper limit of the electrolyte concentration is independently selected from 0.6M, 0.7M, 0.8M, 0.9M, 1M; the lower limit of the electrolyte concentration is independently selected from 0.01M, 0.05M, 0.1M, 0.3M, 0.5M.
In step S200, the electro-activation method includes a method capable of applying a positive potential for oxidation, such as cyclic voltammetry, linear voltammetry, galvanostatic method, chronopotentiometry, and the like, to convert the cobalt sulfide precursor into cobalt oxyhydroxide. In order to ensure the catalytic performance and stability of the product, the electric activation speed is not too fast, and the time is not too short or too long.
Preferably, cyclic voltammetry or linear voltammetry is used, and preferably, the electroactive parameters are: and (3) activating for 0.5-4 h under a voltage window of-0.3V vs.RHE-1.4V vs.RHE.
Specifically, the upper limit of the window voltage is independently selected from 0.8v vs.rhe, 0.9v vs.rhe, 1.0v vs.rhe, 1.2v vs.rhe, 1.4v vs.rhe; the lower limit of the window voltage is independently selected from-0.3vvs.RHE, -0.2V vs.RHE, -0.1V vs.RHE, 0.5V vs.RHE, 0.7V vs.RHE.
Specifically, the upper limit of the activation time is independently selected from 2h, 2.5h, 3h, 3.5h, 4h; the lower limit of the activation time is independently selected from 0.5h, 0.75h, 1h, 1.25h and 1.5h.
Preferably, the conditions for galvanostatic activation are: is provided withThe constant current density is 0.1-100 mA/cm 2 And activating by constant current for 1-60 min until the potential is stable.
Specifically, the upper limit of the current density is independently selected from 50mA/cm 2 、60mA/cm 2 、70mA/cm 2 、80mA/cm 2 、100mA/cm 2 (ii) a The lower limit of the current density is independently selected from 0.1mA/cm 2 、1mA/cm 2 、10mA/cm 2 、20mA/cm 2 、30mA/cm 2 。
Specifically, the upper limit of the activation time is independently selected from 25min, 30min, 40min, 50min, 60min; the lower limit of the activation time is independently selected from 1min, 5min, 10min, 15min, and 20min.
Preferably, the conditions for chronopotentiometric electro-activation are: keeping the current in the potential range of 1-1.6V (relative to the reversible hydrogen electrode) and keeping for 1-60 min.
Specifically, the upper potential range is independently selected from 1.3V, 1.35V, 1.4V, 1.5V, 1.6V; the lower limit of the potential range is independently selected from 1.0V, 1.1V, 1.15V, 1.2V and 1.25V.
Specifically, the upper limit of the activation time is selected from 25min, 30min, 40min, 50min, 60min; the lower limit of the activation time is selected from 1min, 5min, 10min, 15min, and 20min.
The surface of the catalyst obtained by activation is soaked with a small amount of electrolyte, and in order to remove the electrolyte, a washing operation is required, preferably, the washing method comprises the following steps: and washing the catalyst for 2-3 times by using deionized water. After the catalyst is washed, drying operation is needed to prolong the service life of the catalyst.
Optionally, the drying conditions are: drying for 6-12 h at 40-60 ℃.
Specifically, the upper limit of the drying temperature is independently selected from 51 ℃, 53 ℃, 55 ℃, 57 ℃ and 60 ℃; the lower limit of the drying temperature is independently selected from 40 deg.C, 42 deg.C, 45 deg.C, 48 deg.C, and 50 deg.C.
Specifically, the upper limit of the drying time is independently selected from 9h, 10h, 10.5h, 11h, 12h; the lower limit of the drying time is independently selected from 6h, 6.5h, 7h, 7.5h, 8h.
The invention has the beneficial effects that:
1) The cobalt catalyst provided by the invention has strong catalytic performance, active components are not easy to aggregate and fall off in the application process, and the catalyst is easy to separate after use.
2) The surface of the self-growing integral hydrangea-shaped nanosphere catalyst is of a three-dimensional structure formed by assembling nanosheets, the specific surface area is high, catalytic active sites can be fully exposed, and the catalytic efficiency is improved. Meanwhile, the number and the thickness of the sheet layers on the surface of the nanospheres can be controlled by adjusting preparation conditions, and effective mass transfer channels are provided for different reactants to meet the needs of various reactions. Compared with the nanometer linear catalyst, the nanometer ball catalyst with the rough surface has better self-supporting performance, is not easy to aggregate in the application process, and has longer service life.
3) According to the preparation method of the cobalt catalyst, the generation of the nano spherical shape is induced through vulcanization, the change of the number and the size of the nano spheres is controlled through the change of the vulcanization condition, and then the nano spheres are activated into the hydrangea-shaped cobalt oxyhydroxide nano spheres without adding an additional template, so that the cost is saved, and the preparation method is innovative.
4) The preparation method of the cobalt catalyst provided by the invention has the advantages of abundant raw materials, simple operation, high production efficiency, high product yield and low cost.
Drawings
FIG. 1 is a scanning electron micrograph of a self-grown monolithic cobalt oxyhydroxide catalyst prepared in example 1 of the present application, having a scale bar of 500 μm;
FIG. 2 is a scanning electron micrograph of a self-grown monolithic cobalt oxyhydroxide catalyst prepared in example 1 of the present application, having a scale bar of 20 μm;
FIG. 3 is a scanning electron micrograph of a self-grown monolithic cobalt oxyhydroxide catalyst prepared in example 1 of the present application, having a scale bar of 1 μm;
FIG. 4 is an EDX elemental distribution plot for a self-grown monolithic cobalt oxyhydroxide catalyst in the form of a hydrangea configuration as prepared in example 1 of the present application; wherein, (a) is cobalt element, and (b) is oxygen element;
FIG. 5 is a transmission electron micrograph of a self-grown monolithic cobalt oxyhydroxide catalyst in the form of a hydrangea of the structure prepared in example 1 of the present application; wherein, (a) the scale bar is 50nm, and (b) the scale bar is 10nm;
FIG. 6 is a selected area electron diffraction pattern of the self-grown monolithic cobalt oxyhydroxide catalyst prepared in example 1 of the present application;
FIG. 7 is a schematic view of an apparatus in accordance with example 11 of the present application;
FIG. 8 is a graph of anodic current density versus voltage for different electrolytes in a three-electrode system with the anodic catalyst of sample 1 prepared in example 1 of the present application;
FIG. 9 is a graph of cathodic current density versus voltage for different electrolytes in a three-electrode system with a cathode catalyst, sample 1, prepared in example 1 of the present application;
FIG. 10 is a graph of current density versus voltage for different electrolytes in a two-electrode system with both cathode catalyst and anode catalyst for sample 1 prepared in example 1 of the present application;
fig. 11 is a graph of the concentration-electric quantity of the raw material BHMF and the anode product in a two-electrode system when sample 1 prepared in example 1 of the present application is used as a cathode catalyst and an anode catalyst at the same time.
List of parts and reference numerals:
1. a power source; 2. an anode; 3. a cathode; 4. an electrolyte; 5. an air duct; 6. a measuring cylinder; 7. a water tank; 8. and (3) water.
Detailed Description
The invention is further illustrated with reference to the following figures and specific examples.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified. The apparatus used in the following examples, unless otherwise specified, was used with the parameters recommended by the manufacturer.
The instruments and parameters used for sample analysis in the examples were as follows:
SEM analysis was performed using a HITACHI S-4800 scanning electron microscope at 8.0 kV.
EDX analysis was performed using a HITACHI S-4800 scanning electron microscope at 20.0 kV.
TEM analysis was performed using a FEI F20 transmission electron microscope at 200 kV.
Selected area electron diffraction analysis was performed using a FEI F20 transmission electron microscope at 200 kV.
Example 1
(1) Placing 1500mg sublimed sulfur powder in corundum boat of tube furnace, sealing, drying at 30 deg.C under 100mL/min nitrogen atmosphere for 2 hr, and removing water.
(2) The 280mg cobalt foam was immersed in absolute ethanol and ultrasonically cleaned for 10min, and then dried at 60 ℃ for 4h.
(3) Putting the dried sublimed sulfur powder obtained in the step (1) and the cobalt foam obtained in the step (2) into a corundum boat of a tubular furnace together, sealing, and introducing high-purity nitrogen as a whole-process protective gas, wherein the flow rate of the nitrogen is 50mL/min; heating to 350 ℃ at the speed of 5 ℃/min, preserving heat for 0.5h, and naturally cooling to room temperature to obtain the precursor. Wherein the mass ratio of the sublimed sulfur powder to the cobalt foam is 5.4:1.
(4) And (3) taking the precursor obtained in the step (3) as an anode, a graphite rod as a cathode, and a mercury/mercury oxide electrode as a reference electrode, assembling the three electrodes into a three-electrode electrolytic cell together, activating the three-electrode electrolytic cell for 1h in a potassium hydroxide solution with the concentration of 1M under the voltage window of-0.3V vs.RHE to 1.4V vs.RHE by using a cyclic voltammetry method, washing the three-electrode electrolytic cell for 2 times by using deionized water, and drying the three-electrode electrolytic cell for 10h at the temperature of 60 ℃ to obtain the self-grown integral hydrangea-shaped cobalt oxyhydroxide nanosphere catalyst which is marked as a sample 1.
Example 2
(1) Placing 1500mg of sublimed sulfur powder in a corundum boat of a tube furnace, sealing, and drying at 30 ℃ for 2h in a nitrogen atmosphere of 100mL/min to remove the contained water.
(2) 500mg of cobalt foam was immersed in absolute ethanol and ultrasonically cleaned for 10min, and then dried at 60 ℃ for 4h.
(3) Putting the dried sublimed sulfur powder obtained in the step (1) and the cobalt foam obtained in the step (2) into a corundum boat of a tubular furnace together, sealing, and introducing high-purity nitrogen as a whole-process protective gas, wherein the flow rate of the nitrogen is 50mL/min; heating to 350 ℃ at the speed of 5 ℃/min, preserving heat for 0.5h, and naturally cooling to room temperature to obtain the precursor. Wherein the mass ratio of the sublimed sulfur powder to the cobalt foam is 3:1.
(4) And (4) jointly assembling the precursor obtained in the step (3) as an anode, a graphite rod as a cathode and a mercury/mercury oxide electrode as a reference electrode into a three-electrode electrolytic cell, activating for 1h in a potassium hydroxide solution with the concentration of 1M under the voltage window of-0.3V vs.RHE-1.4V vs.RHE by using a cyclic voltammetry method, washing for 2 times by using deionized water, and drying for 10h at the temperature of 60 ℃ to obtain the self-grown integral hydrangea-shaped cobalt oxyhydroxide nanosphere catalyst, which is recorded as a sample 2.
Compared with the example 1, the mass of the carrier used in the example is changed, the rest preparation conditions are not changed, and the quantity of the cobalt oxyhydroxide nanospheres of the finally obtained catalyst is reduced along with the increase of the mass of the carrier.
Example 3
(1) Placing 500mg of sublimed sulfur powder in a corundum boat of a tube furnace, sealing, and drying at 30 ℃ for 2h in a nitrogen atmosphere of 100mL/min to remove contained water.
(2) The 250mg cobalt foam is immersed in absolute ethyl alcohol for ultrasonic cleaning for 10min and then dried for 4h at 60 ℃.
(3) Putting the dried sublimed sulfur powder obtained in the step (1) and the cobalt foam obtained in the step (2) into a corundum boat of a tubular furnace together, sealing, and introducing high-purity nitrogen as a whole-process protective gas, wherein the flow rate of the nitrogen is 50mL/min; heating to 350 ℃ at the speed of 5 ℃/min, preserving heat for 0.5h, and naturally cooling to room temperature to obtain the precursor. Wherein the mass ratio of the sublimed sulfur powder to the cobalt foam is 2:1.
(4) And (3) taking the precursor obtained in the step (3) as an anode, a graphite rod as a cathode, and a mercury/mercury oxide electrode as a reference electrode, assembling the three electrodes into a three-electrode electrolytic cell together, activating the three-electrode electrolytic cell for 1h in a potassium hydroxide solution with the concentration of 1M under the voltage window of-0.3V vs.RHE to 1.4V vs.RHE by using a cyclic voltammetry method, washing the three-electrode electrolytic cell for 2 times by using deionized water, and drying the three-electrode electrolytic cell for 10h at the temperature of 60 ℃ to obtain the self-grown integral hydrangea-shaped cobalt oxyhydroxide nanosphere catalyst which is marked as a sample 3.
Compared with the example 1, the quality of the sulfur source used in the example is changed, the other preparation conditions are not changed, and the quantity of the cobalt oxyhydroxide nanospheres of the finally obtained catalyst is reduced along with the reduction of the quality of the sulfur source.
Example 4
(1) Placing 1500mg of sublimed sulfur powder in a corundum boat of a tube furnace, sealing, and drying at 30 ℃ for 4h in a nitrogen atmosphere of 100mL/min to remove water.
(2) 350mg of cobalt foam was immersed in absolute ethanol and ultrasonically cleaned for 10min, and then dried at 60 ℃ for 4h.
(3) Putting the dried sublimed sulfur powder obtained in the step (1) and the cobalt foam obtained in the step (2) into a corundum boat of a tubular furnace together, sealing, and introducing high-purity nitrogen as a whole-process protective gas, wherein the flow rate of the nitrogen is 100mL/min; heating to 350 ℃ at the speed of 5 ℃/min, preserving heat for 1h, and naturally cooling to room temperature to obtain the precursor. Wherein the mass ratio of the sublimed sulfur powder to the cobalt foam is 4.3:1.
(4) And (3) taking the precursor obtained in the step (3) as an anode, a graphite rod as a cathode, and a mercury/mercury oxide electrode as a reference electrode, assembling the three electrodes into a three-electrode electrolytic cell together, activating the three-electrode electrolytic cell for 1.5h in a potassium hydroxide solution with the concentration of 1M under the voltage window of-0.3V vs.RHE to 1.4V vs.RHE by using a cyclic voltammetry method, washing the three-electrode electrolytic cell for 2 times by using deionized water, and drying the three-electrode electrolytic cell for 12h at the temperature of 60 ℃ to obtain the self-grown integral hydrangea-shaped cobalt oxyhydroxide nanosphere catalyst which is recorded as a sample 4.
Example 5
(1) 1000mg of sodium sulfide powder is put into a corundum boat of a tube furnace, and after sealing, the powder is dried for 5 hours at 30 ℃ in a nitrogen atmosphere of 100mL/min, and the contained water is removed.
(2) The 250mg cobalt foam is immersed in absolute ethyl alcohol for ultrasonic cleaning for 10min and then dried for 4h at 60 ℃.
(3) Putting the dried sodium sulfide powder obtained in the step (1) and the cobalt foam obtained in the step (2) into a corundum boat of a tubular furnace together, sealing, and introducing high-purity argon as a whole-process protective gas, wherein the flow of the argon is 50mL/min; heating to 350 ℃ at the speed of 5 ℃/min, preserving heat for 0.5h, and naturally cooling to room temperature to obtain the precursor. Wherein the mass ratio of the sodium sulfide powder to the cobalt foam is 4:1.
(4) And (3) taking the precursor obtained in the step (3) as an anode, a graphite rod as a cathode, and a mercury/mercury oxide electrode as a reference electrode, assembling the three electrodes into a three-electrode electrolytic cell together, activating the three-electrode electrolytic cell for 1h in a sodium hydroxide solution with the concentration of 1M by using a cyclic voltammetry under a voltage window of-0.3V vs.RHE to 1.4V vs.RHE, washing the three-electrode electrolytic cell for 3 times by using deionized water, and drying the three-electrode electrolytic cell for 10h at the temperature of 60 ℃ to obtain the self-grown integral hydrangea-shaped cobalt oxyhydroxide nanosphere catalyst which is marked as a sample 5.
Example 6
(1) 1500mg of thiourea powder was placed in a corundum boat in a tube furnace, sealed and dried at 30 ℃ for 5 hours in a nitrogen atmosphere of 100mL/min to remove the water content.
(2) 300mg of cobalt foam was immersed in absolute ethanol and ultrasonically cleaned for 10min, and then dried at 60 ℃ for 4h.
(3) Placing the dried thiourea powder obtained in the step (1) and the cobalt foam obtained in the step (2) in a corundum boat of a tubular furnace together, sealing, and introducing high-purity argon as a whole-course protective gas, wherein the flow of the argon is 40mL/min; heating to 300 ℃ at the speed of 6.5 ℃/min, preserving the heat for 1h, and naturally cooling to room temperature to obtain the precursor. Wherein the mass ratio of the thiourea powder to the cobalt foam is 3:1.
(4) And (3) taking the precursor obtained in the step (3) as an anode, a graphite rod as a cathode, and a mercury/mercury oxide electrode as a reference electrode, assembling the three electrodes into a three-electrode electrolytic cell together, activating the three-electrode electrolytic cell for 2h in a potassium hydroxide solution with the concentration of 1M under the voltage window of-0.3V vs.RHE to 1.4V vs.RHE by using a cyclic voltammetry method, washing the three-electrode electrolytic cell for 3 times by using deionized water, and drying the three-electrode electrolytic cell for 8h at the temperature of 60 ℃ to obtain the self-grown integral hydrangea-shaped cobalt oxyhydroxide nanosphere catalyst which is marked as a sample 6.
Example 7
(1) Placing 1500mg of sublimed sulfur powder in a corundum boat of a tube furnace, sealing, and drying at 30 ℃ for 3h in a nitrogen atmosphere of 100mL/min to remove the contained water.
(2) The 400mg cobalt sheet is immersed in absolute ethyl alcohol for ultrasonic cleaning for 10min, and then dried for 4h at 60 ℃.
(3) Putting the dried sublimed sulfur powder obtained in the step (1) and the cobalt sheet obtained in the step (2) into a corundum boat of a tubular furnace together, sealing, and introducing high-purity argon gas as whole-process protective gas, wherein the flow rate of the argon gas is 80mL/min; heating to 400 ℃ at the speed of 8 ℃/min, preserving heat for 0.5h, and naturally cooling to room temperature to obtain the precursor. Wherein the mass ratio of the sublimed sulfur powder to the cobalt sheet is 3.8:1.
(4) And (3) taking the precursor obtained in the step (3) as an anode, a graphite rod as a cathode, and a mercury/mercury oxide electrode as a reference electrode, assembling the three electrodes into a three-electrode electrolytic cell together, activating the three-electrode electrolytic cell for 2h in a potassium hydroxide solution with the concentration of 1M under the voltage window of-0.3V vs.RHE to 1.4V vs.RHE by using a cyclic voltammetry method, washing the three-electrode electrolytic cell for 3 times by using deionized water, and drying the three-electrode electrolytic cell for 8h at the temperature of 60 ℃ to obtain the self-grown integral hydrangea-shaped cobalt oxyhydroxide nanosphere catalyst which is marked as a sample 7.
Example 8
(1) 1200mg of sublimed sulfur powder is placed in a corundum boat of a tube furnace, and after sealing, the powder is dried for 4 hours at 30 ℃ in a nitrogen atmosphere of 100mL/min, and the contained water is removed.
(2) 400mg of cobalt foil was immersed in absolute ethanol and ultrasonically cleaned for 10min, and then dried at 60 ℃ for 4h.
(3) Putting the dried sublimed sulfur powder obtained in the step (1) and the cobalt foil obtained in the step (2) into a corundum boat of a tubular furnace together, sealing, and introducing high-purity argon gas as whole-process protective gas, wherein the flow of the argon gas is 50mL/min; heating to 350 ℃ at the speed of 7 ℃/min, preserving heat for 1h, and naturally cooling to room temperature to obtain the precursor. Wherein the mass ratio of the sublimed sulfur powder to the cobalt foil is 3:1.
(4) Taking the precursor obtained in the step (3) as an anode, a graphite rod as a cathode and a mercury/mercury oxide electrode as a reference electrode, assembling the precursor and the graphite rod into a three-electrode electrolytic cell together, and introducing 5mA/cm in a potassium hydroxide solution with the concentration of 1M in a constant current manner 2 After the current density is activated until the potential is stable and kept for 10min, the mixture is washed by deionized water for 2 times and dried at 50 ℃ for 12h to obtain the self-growing integral hydrangea-shaped cobalt oxyhydroxide nanosphere catalystAgent, noted sample 8.
Example 9
(1) Placing 1500mg of sublimed sulfur powder in a corundum boat of a tube furnace, sealing, and drying at 30 ℃ for 3h in a nitrogen atmosphere of 100mL/min to remove the contained water.
(2) The 500mg cobalt sheet is immersed in absolute ethyl alcohol for ultrasonic cleaning for 10min, and then dried for 4h at 60 ℃.
(3) Putting the dried sublimed sulfur powder obtained in the step (1) and the cobalt sheet obtained in the step (2) into a corundum boat of a tubular furnace together, sealing, and introducing high-purity argon gas as whole-process protective gas, wherein the flow of the argon gas is 60mL/min; heating to 380 ℃ at the speed of 5 ℃/min, preserving the heat for 1h, and naturally cooling to room temperature to obtain the precursor. Wherein the mass ratio of the sublimed sulfur powder to the cobalt sheet is 3:1.
(4) And (3) taking the precursor obtained in the step (3) as an anode, a graphite rod as a cathode, and a mercury/mercury oxide electrode as a reference electrode, jointly assembling the three electrodes into a three-electrode electrolytic cell, activating the three-electrode electrolytic cell in a potassium hydroxide solution with the concentration of 1M for 60min under a voltage window of 1.4V (relative to a reversible hydrogen electrode) by a chronopotentiometry method, washing the three-electrode electrolytic cell with deionized water for 3 times, drying the three-electrode electrolytic cell at 40 ℃ for 12h to obtain the self-grown integral hydrangeal-shaped cobalt oxyhydroxide nanosphere catalyst, and marking the catalyst as a sample 9.
Example 10
Fig. 1 is a scanning electron microscope image of a sample 1, and it can be seen from the image that the microstructure of the catalyst is a hydrangea-shaped nanosphere, and the surface of the nanosphere is formed by a three-dimensional structure assembled by nanosheets, so that the catalyst has good mechanical properties.
Fig. 2 is an element distribution diagram in the EDX test of sample 1, and it can be seen from the figure that cobalt element and oxygen element are uniformly distributed.
Fig. 3 is a transmission electron microscope image of the sample 1, and it can be seen from the image that the nanoparticle surface of the catalyst is formed by a three-dimensional structure assembled by nanosheets, and the characterization result is consistent with the scanning electron microscope image result.
Fig. 4 is a selected area electron diffraction diagram of sample 1, in which the electron diffraction rings correspond to (0 2), (2 4 0), (1 4 0), and (0 2) planes of the cobalt oxyhydroxide standard card 26-0480, respectively, and the catalyst phase is proved to be cobalt oxyhydroxide.
SEM images, element distribution diagrams and TEM images of samples 2 to 9 are similar to sample 1, and only the number of nanospheres is different from the size of nanospheres.
The selected area electron diffraction patterns of samples 2 to 9 were consistent with sample 1, demonstrating that the catalyst phases were all cobalt oxyhydroxide.
Example 11
Preparing a working electrode: respectively fixing the samples 1-9 and pure cobalt foam through stainless steel electrode clamps to prepare the working electrode.
Counter electrode: the graphite rod was used as a counter electrode.
Three-electrode electrolytic cell: the working electrode was used as the anode, the counter electrode as the cathode, and the mercury/mercury oxide electrode as the reference electrode, fixed in a teflon plug, and fixed on a 10mL reaction cell.
Two-electrode symmetrical electrolytic cell: the cathode and the anode are two same working electrodes, and the volume of the reactor is more than 10 mL.
Under the conditions of normal temperature and normal pressure, the assembled two-electrode system is utilized, the voltage of the electrolytic cell is controlled to be 1.7V, and the electrocatalysis performance test is respectively carried out by using potassium hydroxide (1M) solution and 10mM BHMF potassium hydroxide (1M) solution.
The test apparatus as shown in fig. 7, an electrolytic cell comprising a power supply 1, an electrolyte 4, an anode 2, a cathode 3 and a current loop was constructed, the electrolyte was placed in a closed reactor, the gas generated at the cathode was introduced into a gas collection apparatus through a gas guide tube 5, and the gas volume was obtained by a water discharge method. The gas collecting device comprises a measuring cylinder 6, the measuring cylinder 6 is filled with water and is inverted in a water tank 7 filled with water 8, and an outlet of the gas guide pipe is positioned in the measuring cylinder 6. When the electrolyte is 10mM BHMF potassium hydroxide (1M), the coupling reaction can be driven by lower voltage.
The samples 1 to 9 are respectively used as anode catalysts to perform electrocatalytic oxidation of 2,5-furandimethanol (BHMF) to prepare 2,5-furandicarboxylic acid (FDCA), and the catalytic effects of the samples are similar and have good catalytic effects. Sample 1 will typically be taken as an example for explanation.
The test results are shown in fig. 8 to 11 using sample 1 as the anode catalyst.
Fig. 8 shows that, in the three-electrode system, the self-grown integral hydrangea-shaped cobalt oxyhydroxide nanosphere catalyst is used as an anode catalyst, has better performance (namely, lower voltage is needed to achieve the same current density, and the curve is closer to the Y axis) than the pure cobalt foam as the anode for oxygen evolution by electrolysis of water, is used for preparing 2,5-furandicarboxylic acid (FDCA) by electrocatalytic oxidation of 2,5-furandimethanol (BHMF), can drive reaction at lower voltage, and has superior performance.
Fig. 9 shows that, in the three-electrode system, the self-grown integral hydrangea-shaped cobalt oxyhydroxide nanosphere catalyst also has the capability of producing hydrogen far better than that of pure cobalt foam as cathode by water electrolysis (namely, the voltage required for reaching the same current density is lower, the curve is closer to the Y axis), and the addition of 10 mbhmf in the electrolyte has no obvious influence on the hydrogen production performance (the curve has no obvious deviation and basically coincides), which indicates that the catalyst has high hydrogen evolution reaction selectivity.
The sample hydrangea-shaped cobalt oxyhydroxide nanosphere catalyst prepared in example 1 is adopted as a cathode catalyst and an anode catalyst to assemble a two-electrode symmetric electrolytic cell, electrocatalysis reaction is carried out in a BHMF-free electrolyte and a BHMF-free electrolyte of 10mM respectively, the result is shown in figure 10, the preparation of FDCA and the production of hydrogen by electrolyzing water by electrocatalysis oxidation of BHMF are carried out simultaneously, the required overpotential is 279mV lower than that of the pure decomposition water (the curve is closer to the Y axis), and the result shows that the BHMF can be oxidized to generate FDCA and the water can be reduced to hydrogen only by lower energy, so that the catalyst has more excellent catalytic performance.
The sample hydrangea-shaped cobalt oxyhydroxide nanosphere catalyst prepared in example 1 is adopted as a cathode catalyst and an anode catalyst to assemble a two-electrode symmetric electrolytic cell, and the result is shown in fig. 11, wherein the anode product comprises HMF, FDCA, HMFCA, FFCA and DFF, and compared with FDCA, the concentrations of HMF, HMFCA, FFCA and DFF at the reaction end point are extremely low, which shows that the catalyst has high selectivity to FDCA, and the high selectivity of FDCA not only ensures the high purity of the product, but also ensures the very high yield of the product. Meanwhile, the FDCA Faraday efficiency is close to 100%, the energy utilization rate is high, and almost no energy is wasted.
Other samples can achieve similar catalytic effect when used as anode catalysts.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (17)
1. A cobalt catalyst, characterized in that the cobalt catalyst comprises a support and a catalytically active species;
the carrier is a cobalt-based substrate material;
the catalytically active material is grown on the surface of the support;
the shape of the catalytic active substance is a hydrangea-shaped nanosphere;
the preparation method of the cobalt catalyst comprises the following steps:
s100, heating and reacting the carrier and a sulfur source in a protective gas atmosphere to obtain a precursor;
s200, electro-activating the precursor in electrolyte to obtain the cobalt catalyst;
the catalytic active substance is cobalt oxyhydroxide;
in step S100, the mass ratio of the sulfur source to the carrier is 2 to 10.
2. The cobalt catalyst as recited in claim 1, wherein the catalytically active material is supported as a cobalt source and grows on the surface of the support as a self-source.
3. The cobalt catalyst of claim 1, wherein the cobalt-based base material is selected from at least one of cobalt foam, cobalt flakes, cobalt foil, cobalt filaments.
4. The cobalt catalyst as claimed in claim 1, wherein the nanospheres have a diameter of 100 to 500nm.
5. The cobalt catalyst as claimed in claim 1, wherein the nanosphere surface sheet thickness is 1 to 10nm.
6. The cobalt catalyst of claim 1, wherein the sulfur source is at least one of sublimed sulfur, sodium sulfide, and thiourea.
7. The cobalt catalyst as claimed in claim 1, wherein the temperature of the heating reaction is 300 ℃ to 400 ℃ and the reaction time is 0.25h to 2h in step S100.
8. The cobalt catalyst according to claim 1, wherein the temperature increase rate of the heating reaction is 5 to 10 ℃/min.
9. The cobalt catalyst according to claim 1, wherein the flow rate of the shielding gas is 10 to 100mL/min.
10. The cobalt catalyst of claim 1, wherein the step S200 is:
and taking the precursor as an anode, performing electric activation in electrolyte, washing and drying to obtain the cobalt catalyst.
11. The cobalt catalyst of claim 1, wherein the electrolyte is at least one of a potassium hydroxide solution and a sodium hydroxide solution.
12. The cobalt catalyst according to claim 1, wherein the concentration of the electrolyte is 0.01M to 1M.
13. The cobalt catalyst of claim 10, wherein the drying conditions are: drying at 40-60 ℃ for 6-12h.
14. The cobalt catalyst according to claim 1, wherein the electroactive method is any one of cyclic voltammetry, linear voltammetry, galvanostatic method, chronopotentiometry.
15. The cobalt catalyst of claim 14, wherein the conditions of cyclic voltammetry or linear voltammetry electroactivation are: and (4) activating for 0.5h to 4h under-0.3V vs. RHE-1.4V vs. RHE voltage window.
16. The cobalt catalyst of claim 14, wherein the galvanostatic electroactivation conditions are: setting the current density to be 0.1 to 100mA/cm 2 And (4) introducing constant current to activate until the potential is stable, and activating for 1 to 60min.
17. The cobalt catalyst of claim 14, wherein the conditions for chronopotentiometric electro-activation are: keeping the current in the potential range of 1 to 1.6V, and keeping the current for 1 to 60min.
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| CN102712493A (en) * | 2009-08-27 | 2012-10-03 | 康宁股份有限公司 | Zinc oxide and cobalt oxide nanostructures and methods of making thereof |
| CN108889314A (en) * | 2018-08-08 | 2018-11-27 | 湖南理工学院 | A kind of In-situ sulphiding nanometer flower ball-shaped Co of foam cobalt4S3@Co liberation of hydrogen material and preparation method |
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| JP2007001809A (en) * | 2005-06-23 | 2007-01-11 | Tanaka Chemical Corp | Cobalt oxyhydroxide particle and method for producing the same |
| CN102712493A (en) * | 2009-08-27 | 2012-10-03 | 康宁股份有限公司 | Zinc oxide and cobalt oxide nanostructures and methods of making thereof |
| CN108889314A (en) * | 2018-08-08 | 2018-11-27 | 湖南理工学院 | A kind of In-situ sulphiding nanometer flower ball-shaped Co of foam cobalt4S3@Co liberation of hydrogen material and preparation method |
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