CN110270353A - The preparation and application of load transitions bimetallic chalcogen compound nano material in situ - Google Patents
The preparation and application of load transitions bimetallic chalcogen compound nano material in situ Download PDFInfo
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- CN110270353A CN110270353A CN201910305387.4A CN201910305387A CN110270353A CN 110270353 A CN110270353 A CN 110270353A CN 201910305387 A CN201910305387 A CN 201910305387A CN 110270353 A CN110270353 A CN 110270353A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 7
- 230000007704 transition Effects 0.000 title abstract description 13
- 150000001786 chalcogen compounds Chemical class 0.000 title abstract description 8
- 238000011065 in-situ storage Methods 0.000 title description 3
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000004744 fabric Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 235000019441 ethanol Nutrition 0.000 claims abstract description 24
- -1 transition metal salt Chemical class 0.000 claims abstract description 20
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000005864 Sulphur Substances 0.000 claims abstract description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 16
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000002604 ultrasonography Methods 0.000 claims abstract description 8
- 230000001052 transient effect Effects 0.000 claims abstract description 7
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical group NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 36
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 17
- 229940010552 ammonium molybdate Drugs 0.000 claims description 17
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 17
- 239000011609 ammonium molybdate Substances 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 16
- 229910001220 stainless steel Inorganic materials 0.000 claims description 14
- 239000010935 stainless steel Substances 0.000 claims description 14
- 239000012456 homogeneous solution Substances 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 229910052711 selenium Inorganic materials 0.000 claims 1
- 239000011669 selenium Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 238000009766 low-temperature sintering Methods 0.000 abstract 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 10
- 150000004770 chalcogenides Chemical class 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006872 improvement Effects 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- 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
- B01J37/08—Heat treatment
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
- C25B11/043—Carbon, e.g. diamond or graphene
- C25B11/044—Impregnation of carbon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
-
- 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
- Y02E60/50—Fuel cells
Abstract
A kind of preparation method of transition bimetallic chalcogen compound elctro-catalyst, belongs to electrocatalysis material synthesis technical field.Sulfide presoma is obtained through hydro-thermal reaction in varing proportions with different transition metal salt and various sulphur sources, selenium powder is adulterated by low sintering method later, obtains the transient metal chalcogenide compound catalyst with excellent electrocatalysis characteristic.Its preparation process the following steps are included: (1) by carbon cloth (3*3cm‑2) successively 10 minutes ultrasonic in acetone, ethyl alcohol, water, it is spare；(2) transition metal salt is mixed in water in proportion with sulphur source, is stirred to uniformly mixed；(3) solution stirred evenly is transferred in reaction kettle and is put into the carbon cloth that ultrasound is crossed, and 180 DEG C are kept for 12 hours；It is cooled to room temperature, carbon cloth taking-up is successively rinsed well with ethyl alcohol, water, it is dry.(4) another transition metal salt is mixed in water in proportion with sulphur source, is stirred to uniformly mixed；(5) solution stirred evenly is transferred in reaction kettle and is put into carbon cloth obtained by step (3), and 180 DEG C are kept for 12 hours；It is cooled to room temperature, carbon cloth taking-up is successively rinsed well with ethyl alcohol, water, it is dry, obtain bimetallic sulfide；(6) by carbon cloth obtained by step (5), low-temperature sintering obtains transition bimetallic chalcogen compound nano material in varing proportions with selenium powder.The catalyst material that the present invention obtains shows preferable electrocatalysis characteristic, and preparation process is simple, low in cost, is suitble to large-scale production.
Description
Technical field
A kind of electrocatalysis material synthesis technical field, and in particular to original position load transitions bimetallic chalcogen compound nanometer material
Expect the preparation and its application of elctro-catalyst.
Background technique
With the continuous improvement of scientific and technological level, requirement of the society to productivity and substance is also being improved, people for a long time with
It is more serious to come air pollution caused by the burning to fossil fuels such as coal, petroleum, natural gases, water pollution.Fossil fuel
There is also the crises of energy shortage.Therefore it is particularly important various clean energy resourcies to be researched and developed.Relative to traditional process for making hydrogen, electrolysis water
Production hydrogen advantages such as simple, high-efficient and sustainable with process, therefore it has broad prospects in Hydrogen Energy application aspect.Electrolysis
Water is made of two half-reactions, is cathode hydrogen evolution and Oxygen anodic evolution respectively.Wherein Oxygen anodic evolution reaction is a four electronics-proton
Coupling reaction needs higher energy (higher overpotential), so that overpotential for oxygen evolution is much higher than the theoretical decomposition voltage of water
(1.23V).The design and synthesis of efficient Oxygen anodic evolution catalyst are the key that improve water electrolysis hydrogen producing efficiency.Currently, noble metal
Nano material iridium and ruthenium have optimal Oxygen anodic evolution activity, but since its reserves is limited, expensive, are not enough to realize business
Change.Therefore, exploitation has excellent catalytic activity, cheap and rich reserves base metal electrolysis water catalysis material to Guan Chong
It wants.
Summary of the invention
Expensive in order to solve noble metal catalyst, reserves are difficult to be widely applied less and non-precious metal catalyst is excessively electric
The problem of high waste of energy in position, the present invention provides a kind of simple load transitions bimetallic chalcogen compound nano materials in situ
Preparation method, solve the technical problem that current transition-metal catalyst preparation method is complicated and electrolysis water activity is not high.
It mainly comprises the steps that
(1) by carbon cloth (3*3cm-2) successively 10 minutes ultrasonic in acetone, ethyl alcohol, water, it is spare；
(2) by transition metal salt①It is mixed in water in proportion with sulphur source, wherein metal salt①Molar ratio with sulphur source is 1:
5, it stirs to being completely dissolved, obtains homogeneous solution；
(3) solution stirred evenly is transferred in the reaction kettle with stainless steel lining bottom and is put into the carbon cloth that ultrasound is crossed, will
Reaction kettle is placed in air dry oven and is kept for 12 hours for 180 DEG C；It is cooled to room temperature, carbon cloth is taken out and is successively rinsed with ethyl alcohol, water
Completely, dry, obtain monometallic sulfide.
(4) by another transition metal salt②It is mixed in water in proportion with sulphur source, wherein metal salt②With mole of sulphur source
Than for 1:6, wherein transition metal salt①Transition metal salt②Ratio be 1:1-6:1, stir to being completely dissolved, obtain uniformly it is molten
Liquid；
(5) solution stirred evenly is transferred in the reaction kettle with stainless steel lining bottom and is put into carbon cloth obtained by step (3),
Reaction kettle is placed in air dry oven and is kept for 12 hours for 180 DEG C；It is cooled to room temperature, carbon cloth is taken out and successively uses ethyl alcohol, Shui Chong
Wash clean, it is dry, obtain bimetallic sulfide.
(6) by carbon cloth obtained by step (5) and selenium powder, mixing low temp is sintered in varing proportions, wherein carbon cloth carried metal total amount
Ratio with selenium powder is 2:1-2:3, under an argon atmosphere, is warming up to 300 DEG C -400 DEG C, calcines 2-8 hours, obtain the mistake
Cross bimetallic chalcogenide materials；
Transition metal salt described in step (1), (4) is cobalt chloride, nickel chloride, ammonium molybdate etc..
Sulphur source described in step (1), (4) is thiocarbamide, sodium sulphate or vulcanized sodium.
Step (1), the metal salt①Molar ratio with sulphur source is 1:5.
Step (4) metal salt②Molar ratio with sulphur source is 1:6, metal salt①And metal salt②Ratio be 1:1-6:1.
The total amount of the metal salt of the load of carbon cloth described in step (6) and the ratio of selenium powder are 2:1-2:3.
The method according to the invention provides a kind of transition bimetallic chalcogen compound Application of micron and urges in preparing electricity
Agent.
The elctro-catalyst is the elctro-catalyst of catalytic fuel cell or electrolytic cell liberation of hydrogen, oxygen evolution reaction.
In general, the above-mentioned technical proposal conceived through the invention compared with prior art, passes through simple hydro-thermal method
It is prepared for transition bimetallic chalcogen compound nanostructured materials catalyst with low sintering method, improves catalytic performance, is reacted
Mild condition, easy to control, reaction process is simple, low in raw material price, is suitable for large-scale production.
Detailed description of the invention
Fig. 1 is the X-ray diffraction schematic diagram (XRD) of the transient metal chalcogenide compound of the embodiment of the present invention 1, shows to be formed
Corresponding molybdenum cobalt chalcogen compound.
Fig. 2 is the scanning electron microscope schematic diagram of the transient metal chalcogenide compound of the embodiment of the present invention 2, is shown two in catalyst
Close interfacial structure is formd between kind metal chalcogenides.
Fig. 3 is the electrochemistry Hydrogen Evolution Performance schematic diagram of the transient metal chalcogenide compound of the embodiment of the present invention 4, and preparation is urged
Agent shows excellent catalytic activity of hydrogen evolution.
Fig. 4 is the Electrochemical oxygen evolution performance schematic diagram of the transient metal chalcogenide compound of the embodiment of the present invention 4, and preparation is urged
Agent shows excellent analysis oxygen catalytic performance.
Fig. 5 is the electrochemistry all-hydrolytic performance schematic diagram of the transient metal chalcogenide compound of the embodiment of the present invention 4, preparation
Catalyst shows excellent electro-catalysis water dispersible energy.
Specific embodiment
The present invention is further illustrated below with reference to embodiment, but the present invention is not limited only to following embodiment.
Embodiment 1
Step 1: by carbon cloth (3*3cm-2) successively 10 minutes ultrasonic in acetone, ethyl alcohol, water, it is spare；
Step 2: ammonium molybdate is mixed in water in proportion with thiocarbamide, wherein the molar ratio of ammonium molybdate and thiocarbamide is 1:5,
The volume of water is that 36ml is stirred to being completely dissolved, and obtains homogeneous solution；
Step 3: the solution stirred evenly is transferred in the reaction kettle with stainless steel lining bottom and is put into the carbon that ultrasound is crossed
Reaction kettle is placed in air dry oven and is kept for 12 hours for 180 DEG C by cloth；It is cooled to room temperature, carbon cloth is taken out and successively uses ethyl alcohol, water
It rinses well, it is dry, obtain monometallic sulfide.
Step 4: cobalt chloride is mixed in water in proportion with thiocarbamide, wherein the molar ratio of cobalt chloride and thiocarbamide is 1:6,
Wherein the ratio of cobalt chloride and ammonium molybdate is 1:1, stirs to being completely dissolved, obtains homogeneous solution；
Step 5: the solution stirred evenly is transferred in the reaction kettle with stainless steel lining bottom and is put into carbon obtained by third step
Reaction kettle is placed in air dry oven and is kept for 12 hours for 180 DEG C by cloth；It is cooled to room temperature, carbon cloth is taken out and successively uses ethyl alcohol, water
It rinses well, it is dry, obtain bimetallic sulfide.
Step 6: by carbon cloth obtained by step (5) and selenium powder, mixing low temp is sintered in varing proportions, wherein carbon cloth carried metal
Total amount and the ratio of selenium powder are 1:1, under an argon atmosphere, are warming up to 300 DEG C, and heating rate is 5 DEG C/min, calcine 2 hours, i.e.,
The transition bimetallic chalcogenide materials are made；
Embodiment 2
Step 1: by carbon cloth (3*3cm-2) successively 10 minutes ultrasonic in acetone, ethyl alcohol, water, it is spare；
Step 2: ammonium molybdate is mixed in water in proportion with thiocarbamide, wherein the molar ratio of ammonium molybdate and thiocarbamide is 1:5,
The volume of water is that 36ml is stirred to being completely dissolved, and obtains homogeneous solution；
Step 3: the solution stirred evenly is transferred in the reaction kettle with stainless steel lining bottom and is put into the carbon that ultrasound is crossed
Reaction kettle is placed in air dry oven and is kept for 12 hours for 180 DEG C by cloth；It is cooled to room temperature, carbon cloth is taken out and successively uses ethyl alcohol, water
It rinses well, it is dry, obtain monometallic sulfide.
Step 4: cobalt chloride is mixed in water in proportion with thiocarbamide, wherein the molar ratio of cobalt chloride and thiocarbamide is 1:6,
Wherein the ratio of ammonium molybdate and cobalt chloride is 1:1, stirs to being completely dissolved, obtains homogeneous solution；
Step 5: the solution stirred evenly is transferred in the reaction kettle with stainless steel lining bottom and is put into carbon obtained by third step
Reaction kettle is placed in air dry oven and is kept for 12 hours for 180 DEG C by cloth；It is cooled to room temperature, carbon cloth is taken out and successively uses ethyl alcohol, water
It rinses well, it is dry, obtain bimetallic sulfide.
Step 6: by carbon cloth obtained by step (5) and selenium powder, mixing low temp is sintered in varing proportions, wherein carbon cloth carried metal
Total amount and the ratio of selenium powder are 2:1, under an argon atmosphere, are warming up to 350 DEG C, and heating rate is 5 DEG C/min, calcine 2 hours, i.e.,
The transition bimetallic chalcogenide materials are made；
Embodiment 3:
Step 1: by carbon cloth (3*3cm-2) successively 10 minutes ultrasonic in acetone, ethyl alcohol, water, it is spare；
Step 2: ammonium molybdate is mixed in water in proportion with thiocarbamide, wherein the molar ratio of ammonium molybdate and thiocarbamide is 1:5,
The volume of water is that 36ml is stirred to being completely dissolved, and obtains homogeneous solution；
Step 3: the solution stirred evenly is transferred in the reaction kettle with stainless steel lining bottom and is put into the carbon that ultrasound is crossed
Reaction kettle is placed in air dry oven and is kept for 12 hours for 180 DEG C by cloth；It is cooled to room temperature, carbon cloth is taken out and successively uses ethyl alcohol, water
It rinses well, it is dry, obtain monometallic sulfide.
Step 4: cobalt chloride is mixed in water in proportion with thiocarbamide, wherein the molar ratio of cobalt chloride and thiocarbamide is 1:6,
Wherein the ratio of ammonium molybdate and cobalt chloride is 1:1, stirs to being completely dissolved, obtains homogeneous solution；
Step 5: the solution stirred evenly is transferred in the reaction kettle with stainless steel lining bottom and is put into carbon obtained by third step
Reaction kettle is placed in air dry oven and is kept for 12 hours for 180 DEG C by cloth；It is cooled to room temperature, carbon cloth is taken out and successively uses ethyl alcohol, water
It rinses well, it is dry, obtain bimetallic sulfide.
Step 6: by carbon cloth obtained by step (5) and selenium powder, mixing low temp is sintered in varing proportions, wherein carbon cloth carried metal
Total amount and the ratio of selenium powder are 2:3, under an argon atmosphere, are warming up to 400 DEG C, and heating rate is 5 DEG C/min, calcine 2 hours, i.e.,
The transition bimetallic chalcogenide materials are made；
Embodiment 4
Step 1: by carbon cloth (3*3cm-2) successively 10 minutes ultrasonic in acetone, ethyl alcohol, water, it is spare；
Step 2: ammonium molybdate is mixed in water in proportion with thiocarbamide, wherein the molar ratio of ammonium molybdate and thiocarbamide is 1:5,
The volume of water is that 36ml is stirred to being completely dissolved, and obtains homogeneous solution；
Step 3: the solution stirred evenly is transferred in the reaction kettle with stainless steel lining bottom and is put into the carbon that ultrasound is crossed
Reaction kettle is placed in air dry oven and is kept for 12 hours for 180 DEG C by cloth；It is cooled to room temperature, carbon cloth is taken out and successively uses ethyl alcohol, water
It rinses well, it is dry, obtain monometallic sulfide.
Step 4: copper chloride is mixed in water in proportion with vulcanized sodium, wherein the molar ratio of copper chloride and vulcanized sodium is
1:6, wherein the ratio of ammonium molybdate and copper chloride is 4:1, stirs to being completely dissolved, obtains homogeneous solution；
Step 5: the solution stirred evenly is transferred in the reaction kettle with stainless steel lining bottom and is put into carbon obtained by third step
Reaction kettle is placed in air dry oven and is kept for 12 hours for 180 DEG C by cloth；It is cooled to room temperature, carbon cloth is taken out and successively uses ethyl alcohol, water
It rinses well, it is dry, obtain bimetallic sulfide.
Step 6: by carbon cloth obtained by step (5) and selenium powder, mixing low temp is sintered in varing proportions, wherein carbon cloth carried metal
Total amount and the ratio of selenium powder are 1:1, under an argon atmosphere, are warming up to 350 DEG C, and heating rate is 5 DEG C/min, calcine 2 hours, i.e.,
The transition bimetallic chalcogenide materials are made；
Embodiment 5
Step 1: by carbon cloth (3*3cm-2) successively 10 minutes ultrasonic in acetone, ethyl alcohol, water, it is spare；
Step 2: ammonium molybdate is mixed in water in proportion with thiocarbamide, wherein the molar ratio of ammonium molybdate and thiocarbamide is 1:5,
The volume of water is that 36ml is stirred to being completely dissolved, and obtains homogeneous solution；
Step 3: the solution stirred evenly is transferred in the reaction kettle with stainless steel lining bottom and is put into the carbon that ultrasound is crossed
Reaction kettle is placed in air dry oven and is kept for 12 hours for 180 DEG C by cloth；It is cooled to room temperature, carbon cloth is taken out and successively uses ethyl alcohol, water
It rinses well, it is dry, obtain monometallic sulfide.
Step 4: nickel chloride is mixed in water in proportion with vulcanized sodium, wherein the molar ratio of nickel chloride and vulcanized sodium is
1:6, wherein the ratio of ammonium molybdate and nickel chloride is 6:1, stirs to being completely dissolved, obtains homogeneous solution；
Step 5: the solution stirred evenly is transferred in the reaction kettle with stainless steel lining bottom and is put into carbon obtained by third step
Reaction kettle is placed in air dry oven and is kept for 12 hours for 180 DEG C by cloth；It is cooled to room temperature, carbon cloth is taken out and successively uses ethyl alcohol, water
It rinses well, it is dry, obtain bimetallic sulfide.
Step 6: by carbon cloth obtained by step (5) and selenium powder, mixing low temp is sintered in varing proportions, wherein carbon cloth carried metal
Total amount and the ratio of selenium powder are 1:1, under an argon atmosphere, are warming up to 350 DEG C, and heating rate is 5 DEG C/min, calcine 2 hours, i.e.,
The transition bimetallic chalcogenide materials are made；
Embodiment 6
By product test liberation of hydrogen, analysis oxygen and the water-splitting performance of embodiment preparation, made carbon cloth is fixed on electrode holder
On work electrode, then using three-electrode method, (for the glass-carbon electrode of preparation for working electrode, reversible hydrogen is reference electrode, carbon-point
For auxiliary electrode) liberation of hydrogen, analysis oxygen and the aqueous energy of complete solution are tested on Shanghai Chen Hua electrochemical workstation.
Claims (6)
1. the preparation and application of transient metal chalcogenide compound nano material, its step are as follows:
(1) by carbon cloth (3*3cm-2) successively 10 minutes ultrasonic in acetone, ethyl alcohol, water, it is spare；
(2) by transition metal salt①It is mixed in water in proportion with sulphur source, wherein metal salt①Molar ratio with sulphur source is 1:5, is stirred
It mixes to being completely dissolved, obtains homogeneous solution；
(3) solution stirred evenly is transferred in the reaction kettle with stainless steel lining bottom and is put into the carbon cloth that ultrasound is crossed, and will react
Kettle is placed in air dry oven and is kept for 12 hours for 180 DEG C；It is cooled to room temperature, carbon cloth taking-up is successively rinsed well with ethyl alcohol, water,
It is dry, obtain monometallic sulfide.
(4) by another transition metal salt②It is mixed in water in proportion with sulphur source, wherein metal salt②Molar ratio with sulphur source is
1:6, wherein transition metal salt①Transition metal salt②Ratio be 1:1-6:1, stir to being completely dissolved, obtain homogeneous solution；
(5) solution stirred evenly is transferred in the reaction kettle with stainless steel lining bottom and is put into carbon cloth obtained by step (3), will be anti-
It answers kettle to be placed in air dry oven to be kept for 12 hours for 180 DEG C；It is cooled to room temperature, carbon cloth is taken out successively to be rinsed with ethyl alcohol, water and is done
Only, dry, obtain bimetallic sulfide.
(6) by carbon cloth obtained by step (5) and selenium powder, mixing low temp is sintered in varing proportions, wherein carbon cloth carried metal total amount and selenium
The ratio of powder is 2:1-2:3, under an argon atmosphere, is warming up to 300 DEG C -400 DEG C, calcines 2-8 hours, it is double to obtain the transition
Metal chalcogenides material.
2. preparation method as described in claim 1, which is characterized in that transition metal salt described in step (1), (4) is chlorine
Change cobalt, nickel chloride, ammonium molybdate etc..
3. preparation method as described in claim 1, it is characterised in that the sulphur source is thiocarbamide, sodium sulphate or vulcanized sodium.
4. preparation method as described in claim 1, it is characterised in that the metal salt①Molar ratio with sulphur source is 1:5, gold
Belong to salt②Molar ratio with sulphur source is 1:6, metal salt①And metal salt②Ratio be 1:1-6:1.
5. preparation method as described in claim 1, it is characterised in that the total amount and selenium powder of the metal salt of the carbon cloth load
Ratio be 2:1-2:3.
6. material as described in claim 1 is applied to elctro-catalyst, which is characterized in that the elctro-catalyst is that liberation of hydrogen is anti-
It answers, the elctro-catalyst of oxygen evolution reaction and water-splitting reaction.
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