CN113457680A - Cobalt catalyst and preparation method thereof - Google Patents
Cobalt catalyst and preparation method thereof Download PDFInfo
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- CN113457680A CN113457680A CN202010242556.7A CN202010242556A CN113457680A CN 113457680 A CN113457680 A CN 113457680A CN 202010242556 A CN202010242556 A CN 202010242556A CN 113457680 A CN113457680 A CN 113457680A
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- cobalt
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- cobalt catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 64
- 239000010941 cobalt Substances 0.000 title claims abstract description 64
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002077 nanosphere Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 26
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- 239000013543 active substance Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- 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 compound 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000003792 electrolyte Substances 0.000 claims description 24
- 239000006260 foam Substances 0.000 claims description 24
- 230000001681 protective effect Effects 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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 11
- 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
- 239000011149 active material Substances 0.000 claims description 6
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 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
- 239000000758 substrate Substances 0.000 abstract description 4
- 239000000843 powder Substances 0.000 description 32
- 239000007789 gas Substances 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 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
- 238000007789 sealing Methods 0.000 description 17
- 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
- DSLRVRBSNLHVBH-UHFFFAOYSA-N HMF alcohol Natural products OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 description 12
- 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
- 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 8
- NSRBDSZKIKAZHT-UHFFFAOYSA-N tellurium zinc Chemical compound [Zn].[Te] NSRBDSZKIKAZHT-UHFFFAOYSA-N 0.000 description 8
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 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
- 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 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 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
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 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
- 150000002431 hydrogen Chemical class 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
- 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
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-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
- 238000006056 electrooxidation reaction 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
- 238000005259 measurement Methods 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
- 238000012546 transfer Methods 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Plasma & Fusion (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
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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 practical cobalt-based catalysts are cobalt oxides, sulfides, borides and the like, and the catalytic capability of the cobalt-based catalysts can be comparable to 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, which comprises 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 shape of the catalytic active substance is a hydrangea-shaped nanosphere.
Optionally, the catalytically active material is grown on the surface of the support from a source of cobalt on the support.
Optionally, the cobalt-based substrate material is selected from at least one of cobalt foam, cobalt sheet, cobalt foil, cobalt filament.
Optionally, the diameter of the nanosphere is 100-500 nm.
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 the 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 4 h.
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 100 mL/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 100 mL/min; the lower flow limit of the protective gas is independently selected from 10mL/min, 20mL/min, 30mL/min, 40mL/min, and 50 mL/min.
Optionally, in step S100, the mass ratio of the sulfur source to the carrier is 2-10: 1;
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: 1; the lower limit of the mass ratio of the sulfur source to the carrier is independently selected from 2:1, 3:1, 3.8:1, 4.3:1 and 5.4: 1.
Optionally, in step S100, the temperature of the heating reaction is 300 ℃ to 400 ℃, and the reaction time is 0.25h to 2 h;
in order to ensure the quality of the product, the heating speed is not required to be 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 and 2 h; the lower limit of the reaction time is independently selected from 0.25h, 0.5h, 0.75h, 1h, 1.25 h.
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 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) under a voltage window of-0.3V vs. RHE-1.4V vs. RHE, activating for 0.5 h-4 h.
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-0.3 Vvs.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, 4 h; the lower limit of the activation time is independently selected from 0.5h, 0.75h, 1h, 1.25h and 1.5 h.
Preferably, the conditions for galvanostatic electroactivation are: setting the current density to 0.1-100 mA/cm2And introducing constant current to activate until the potential is stable, and activating for 1-60 min.
Specifically, the upper limit of the current density is independently selected from 50mA/cm2、60mA/cm2、70mA/cm2、80mA/cm2、100mA/cm2(ii) a The lower limit of the current density is independently selected from 0.1mA/cm2、1mA/cm2、10mA/cm2、20mA/cm2、30mA/cm2。
Specifically, the upper limit of the activation time is independently selected from 25min, 30min, 40min, 50min, 60 min; the lower limit of the activation time is independently selected from 1min, 5min, 10min, 15min and 20 min.
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 limit 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, 60 min; the lower limit of the activation time is selected from 1min, 5min, 10min, 15min, and 20 min.
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, 12 h; the lower limit of the drying time is independently selected from 6h, 6.5h, 7h, 7.5h and 8 h.
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 nanosphere can be controlled by adjusting the preparation conditions, and effective mass transfer channels are provided for different reactants to meet the requirements 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 rich raw materials, simple operation and high production efficiency, and the product prepared by the method has high 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 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 prepared in example 1 of the present application; wherein, (a) the scale bar is 50nm, and (b) the scale bar is 10 nm;
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 the structure of an apparatus according to 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 all 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 of sublimed sulfur powder in a corundum boat of a tube furnace, sealing, and drying at 30 ℃ in a nitrogen atmosphere of 100mL/min for 2h to remove the contained water.
(2) The 280mg cobalt foam was immersed in absolute ethanol and ultrasonically cleaned for 10min, and then dried at 60 ℃ for 4 h.
(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 50 mL/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, jointly assembling the three electrodes into a three-electrode electrolytic cell, activating the three electrodes for 1h in a potassium 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 electrodes for 2 times by using deionized water, and drying the three electrodes for 10h at the temperature of 60 ℃ to obtain the self-grown integral hydrangeal-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 ℃ in a nitrogen atmosphere of 100mL/min for 2h to remove the contained water.
(2) The 500mg cobalt foam was immersed in absolute ethanol and ultrasonically cleaned for 10min, and then dried at 60 ℃ for 4 h.
(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 50 mL/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 (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 electrodes for 1h in a potassium 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 electrodes for 2 times by using deionized water, and drying the three electrodes for 10h at the temperature of 60 ℃ to obtain the self-grown integral hydrangeal-shaped cobalt oxyhydroxide nanosphere catalyst which is marked as a sample 2.
Compared with the example 1, the carrier mass 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 carrier mass.
Example 3
(1) Placing 500mg of sublimed sulfur powder in a corundum boat of a tube furnace, sealing, and drying at 30 ℃ for 2 hours 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 50 mL/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, jointly assembling the three electrodes into a three-electrode electrolytic cell, activating the three electrodes for 1h in a potassium 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 electrodes for 2 times by using deionized water, and drying the three electrodes for 10h at the temperature of 60 ℃ to obtain the self-grown integral hydrangeal-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 the contained water.
(2) 350mg of cobalt foam was immersed in absolute ethanol and ultrasonically cleaned for 10min, and then dried at 60 ℃ for 4 h.
(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 100 mL/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, jointly assembling the three electrodes into a three-electrode electrolytic cell, activating the three electrodes for 1.5h in a potassium 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 electrodes for 2 times by using deionized water, and drying the three electrodes for 12h at the temperature of 60 ℃ to obtain the self-grown integral hydrangeal-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 50 mL/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, jointly assembling the three electrodes into a three-electrode electrolytic cell, activating the three electrodes 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 electrodes for 3 times by using deionized water, and drying the three electrodes for 10h at the temperature of 60 ℃ to obtain the self-grown integral hydrangeal-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) The 300mg cobalt foam was immersed in absolute ethanol and ultrasonically cleaned for 10min, and then dried at 60 ℃ for 4 h.
(3) Putting the dried thiourea 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-course protective gas, wherein the flow rate of the argon is 40 mL/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, jointly assembling the three electrodes into a three-electrode electrolytic cell, activating the three electrodes for 2h in a potassium 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 electrodes with deionized water for 3 times, and drying the three electrodes for 8h at the temperature of 60 ℃ to obtain the self-grown integral hydrangeal-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 80 mL/min; heating to 400 ℃ at the speed of 8 ℃/min, preserving the 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, jointly assembling the three electrodes into a three-electrode electrolytic cell, activating the three electrodes for 2h in a potassium 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 electrodes with deionized water for 3 times, and drying the three electrodes for 8h at the temperature of 60 ℃ to obtain the self-grown integral hydrangeal-shaped cobalt oxyhydroxide nanosphere catalyst which is marked as a sample 7.
Example 8
(1) 1200mg of sublimed sulfur powder is put into 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 to remove the contained water.
(2) The 400mg cobalt foil was immersed in absolute ethanol and ultrasonically cleaned for 10min, and then dried at 60 ℃ for 4 h.
(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 50 mL/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 manner2After the current density is activated until the potential is stable and kept for 10min, the catalyst is washed for 2 times by deionized water, and the catalyst is dried for 12h at 50 ℃ to obtain the self-growing integral hydrangea-shaped cobalt oxyhydroxide nanosphere catalyst which is marked as a 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 60 mL/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 of EDX measurement of sample 1, and it is understood from the figure that cobalt and oxygen 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 nanosphere 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 the selected area electron diffraction diagram of sample 1, in which the electron diffraction rings correspond to (002), (240), (140), and (021) planes of the standard card 26-0480 of cobalt oxyhydroxide, 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 the 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 collection 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 the 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.
And respectively taking samples 1-9 as anode catalysts to perform electrocatalytic oxidation on 2, 5-furandimethanol (BHMF) to prepare 2, 5-furandicarboxylic acid (FDCA) for testing, wherein 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 reach the same current density, 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 BHMF-free electrolyte and 10mM BHMF-free electrolyte respectively, the result is shown in figure 10, electrocatalysis oxidation is carried out on BHMF to prepare FDCA and electrolyze water to produce hydrogen, the required overpotential is 279mV lower than that of the pure decomposition water (the curve is closer to the Y axis), and the lower energy is only needed to oxidize BHMF to generate FDCA and reduce water to hydrogen, so that the catalyst has more excellent catalytic performance.
The sample hydrangea-shaped cobalt oxyhydroxide nanosphere catalyst prepared in example 1 is used as a cathode catalyst and an anode catalyst to assemble a two-electrode symmetric electrolytic cell, and the electrochemical oxidation of BHMF is performed to prepare FDCA, so that the result is shown in FIG. 11, the anode product comprises HMF, FDCA, HMFCA, FFCA and DFF, and compared with FDCA, the concentration of HMF, HMFCA, FFCA and DFF at the reaction endpoint is extremely low, which shows that the catalyst has high selectivity to FDCA, and the high FDCA selectivity 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 (10)
1. A cobalt catalyst comprising a support and a catalytically active material;
the carrier is a cobalt-based base 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.
2. The cobalt catalyst as claimed in claim 1, wherein the catalytically active material is grown on the surface of the support as a cobalt source, 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 500 nm;
preferably, the thickness of the nanosphere surface sheet layer is 1-10 nm.
5. A cobalt catalyst according to any one of claims 1 to 4, characterised in that the catalytically active species is cobalt oxyhydroxide.
6. A process for preparing a cobalt catalyst as claimed in any one of claims 1 to 5, characterized in that it comprises at least:
s100, heating and reacting the carrier and the sulfur source in a protective gas atmosphere to obtain a precursor;
and S200, electro-activating the precursor in an electrolyte to obtain the cobalt catalyst.
7. The method according to claim 6, wherein in step S100, the mass ratio of the sulfur source to the carrier is 2-10: 1;
preferably, the sulfur source is at least one of sublimed sulfur, sodium sulfide and thiourea.
8. The preparation method according to claim 6, wherein in step S100, the temperature of the heating reaction is 300 ℃ to 400 ℃, and the reaction time is 0.25h to 2 h;
preferably, the heating rate of the heating reaction is 5-10 ℃/min;
preferably, the flow rate of the protective gas is 10mL/min to 100 mL/min.
9. The method according to claim 6, wherein the step S200 is:
taking the precursor as an anode, performing electric activation in electrolyte, washing and drying to obtain the cobalt catalyst;
preferably, the electrolyte is at least one of potassium hydroxide solution and sodium hydroxide solution;
preferably, the concentration of the electrolyte is 0.01M-1M;
preferably, the drying conditions are: drying for 6-12 h at 40-60 ℃.
10. The production method according to claim 9, wherein the electro-activation method is any one of cyclic voltammetry, linear voltammetry, galvanostatic method, chronopotentiometry;
preferably, the cyclic voltammetry or linear voltammetry electroactive conditions are: activating for 0.5-4 h under a voltage window of-0.3V vs. RHE-1.4V vs. RHE;
preferably, the conditions for galvanostatic electroactivation are: setting the current density to 0.1-100 mA/cm2Activating by constant current until the potential is stable, and activating for 1-60 min;
preferably, the conditions for chronopotentiometric electro-activation are: keeping the current in the range of 1-1.6V potential and keeping for 1-60 min.
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