CN105688941B - A kind of Cu7S4@MoS2Heterogeneous nanometer framework material and its application of catalytic electrolysis water hydrogen manufacturing - Google Patents
A kind of Cu7S4@MoS2Heterogeneous nanometer framework material and its application of catalytic electrolysis water hydrogen manufacturing Download PDFInfo
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- CN105688941B CN105688941B CN201610020477.5A CN201610020477A CN105688941B CN 105688941 B CN105688941 B CN 105688941B CN 201610020477 A CN201610020477 A CN 201610020477A CN 105688941 B CN105688941 B CN 105688941B
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- presoma
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a kind of Cu7S4@MoS2Heterogeneous nanometer framework material and its application of catalytic electrolysis water hydrogen manufacturing.The present invention is using the method for thermally decomposing presoma, with Cu7S4For support frame, pass through MoS2Etching has obtained surface and has been rich in active edge site, the extra small annular Cu with pole high activity and stability7S4@MoS2Heterogeneous nanometer mount structure mixes with C powder after removing its surface ligand, is then coated with being applied to catalytic electrolysis water hydrogen manufacturing on the electrode.As a kind of non-precious metal catalyst, since it is with good crystallinity and rich in MoS2Active edge site can reduce the deposition potential of hydrogen in water, platinum can be substituted as effective electrocatalytic hydrogen evolution material, when current density reaches 10mA/cm2And 200mA/cm2When, overpotential is only respectively 133mV and 206mV, in the MoS reported2Most highly active and high stability are shown in nanocatalyst.Since solvent-thermal method can reasonably be extended, the present invention opens new road for the other non-noble metal sulfided object catalyst of a large amount of development.
Description
Technical field
It is more particularly to a kind of with high catalytic hydrogen evolution activity the invention belongs to technical field of nanometer material preparation
Cu7S4@MoS2Nano-heterogeneous structure framework material can be applied to catalytic electrolysis aquatic products hydrogen.
Background technology
The evolving hydrogen reaction of basic step as electrolysis water needs effective and inexpensive catalyst to reach in practice
To quick dynamic process.All the time, Pt is considered as the best electrolysis water liberation of hydrogen catalyst of activity, however the low of it contains
Amount and its widespread adoption of expensive price limit.Liberation of hydrogen catalysis as a very promising cheap replacement Pt
Agent, the MoS of nanostructured2Extensive research is obtained.So far, Many researchers confirm through a large number of experiments with calculating
The MoS of stratiform2Catalytic activity be located at its edge site, and positioned at edge unsaturated S atom in catalytic hydrogen evolution reaction
Play important function.This reason is based on, researcher has attempted various methods and gone to improve nanometer MoS2Exposed activity
Number of loci.
Recently due to unbodied MoS2Comprising many unsaturated S atoms of activity, can effectively catalytic hydrogen evolution react, because
This has attracted the concern of scientist.However, unbodied S atom has very poor crystallinity, result in it has phase in acid
To the electrochemical stability of high dissolubility and difference, so as to limit its practical application.Therefore, in order to simultaneously reach high analysis
Hydrogen activity and long-time stability, one existing abundant active edge site of development have very high crystalline MoS again2It receives
Rice catalyst is an effective method.
Invention content
To meet the needs of energy industry field, being specifically designed one kind, there is the present invention high catalysis to produce hydrogen activity and stabilization
The extra small circular ring shape Cu of property7S4@MoS2Heterogeneous nanometer mount structure can be applied to catalytic electrolysis water hydrogen manufacturing.
The present invention is using the method for thermally decomposing presoma, with Cu7S4For support frame, pass through MoS2Etching has obtained surface
Cu rich in active edge site, the extra small annular with pole high activity and stability7S4@MoS2Heterogeneous nanometer mount structure, is removed
It goes after its surface ligand and C powder mixes, be then coated with being applied to catalytic electrolysis water hydrogen manufacturing on the electrode.
Cu of the present invention7S4@MoS2The preparation method of heterogeneous nanometer framework material, is as follows：
A. 4-6ml oleyl amines and 4-6ml octadecylenes are stirred, then add in 0.1-0.5mmol Cu presoma and
The presoma of the S of 20-140mg after 190-210 DEG C keeps 10-20min, continues to be heated to add in 0.2- at 260-310 DEG C
The presoma of the presoma of the Mo of 1mmol and the S of 0.4-2mmol keeps 5-30min at 275-300 DEG C；
B. after reacting natural cooling, 5000-15000 revs/min of centrifugation 5-20min of reaction solution is taken out, precipitation is dispersed in just
In hexane；
C. the C powder of 1-10mg is distributed in n-hexane, be then added in the dispersion liquid of step b, ultrasonic 30-90min
Afterwards, 5000-15000 revs/min of centrifugation 5-20min, obtains being supported on nanocrystalline on C powder；
D. by be supported on C powder it is nanocrystalline be distributed in the acetic acid of 20-50mL, 10-20h is stirred at 40-80 DEG C and is removed
Surface ligand, 5000-15000 revs/min of centrifugation 5-20min, obtains Cu7S4@MoS2Heterogeneous nanometer framework material, distributes it to
The in the mixed solvent of water and isopropanol.
The presoma of the Cu is selected from copper chloride, acetylacetone copper, copper nitrate.
The presoma of the Mo is selected from：Mo(CO)6、Mo(NO3)3·H2O、MoCl5。
The presoma of the S is selected from：Lauryl mercaptan, S powder, N, N- dibutyl dithio formic acid.
By the above-mentioned Cu being prepared7S4@MoS2Heterogeneous nanometer framework material is applied to catalytic electrolysis water hydrogen manufacturing.It is specific anti-
Answer condition：Perfluorinated sulfonic acid solution is added in the dispersion liquid that step b is obtained, is then coated on glass-carbon electrode, work is used as after dry
Make electrode, in the H of 0.5M2SO4In solution, under nitrogen protective condition, using glass carbon-point as to electrode, saturation calomel is reference electricity
Pole carries out catalytic electrolysis water hydrogen production reaction with three-electrode system.
Beneficial effects of the present invention：The invention discloses a kind of simple methods to obtain having cricoid Cu7S4@MoS2It is different
Matter nanometer framework material.As a kind of non-precious metal catalyst, since it is with good crystallinity and rich in MoS2Active edge
Edge site can reduce the deposition potential of hydrogen in water, can substitute platinum as effective electrocatalytic hydrogen evolution material, work as current density
Reach 10mA/cm2And 200mA/cm2When, overpotential is only respectively 133mV and 206mV, in the MoS reported2Nanometer is urged
Most highly active and high stability are shown in agent.Since solvent-thermal method can reasonably be extended, the present invention is a large amount of hairs
The other non-noble metal sulfided object catalyst of exhibition open new road.
Description of the drawings
Fig. 1：Cu7S4@MoS2Electron microscope, high resolution electron microscopy figure and the corresponding first vegetarian noodles surface sweeping of heterogeneous nanometer framework material
Picture.
Specific embodiment
Embodiment 1
A. 6ml oleyl amines (OAM), 4ml octadecylenes (ODE) are stirred, add in the Cu (NO of 0.1mmol3)2·3H2O and
20mg N, N- dibutyl-dithiocarbonic acids, 15min is kept at 190 DEG C, to synthesize obtained Cu7S4Nano particle is skeleton,
Continue to heat the MoCl that 0.2mmol is injected at 300 DEG C5With the S powder of 0.4mmol, constant temperature keeps 20min at 300 DEG C；
B. after reacting natural cooling, reaction solution centrifugation (12000 revs/min) 10min is taken out, retains precipitation n-hexane dissolution
It collects；
C. the C powder of 4mg is distributed in n-hexane, be then added in the dispersion liquid of step b, after ultrasonic 80min, centrifugation
(12000 revs/min) 10min must be supported on nanocrystalline on C powder；
D. by be supported on C powder it is nanocrystalline be distributed in the acetic acid of 40mL, 15h is stirred at 70 DEG C and removes surface ligand,
(12000 revs/min) 15min is centrifuged, obtains Cu7S4@MoS2Heterogeneous nanometer framework material, is re-dispersed into 1000ul bodies
Product is than being 1:1 water and the in the mixed solvent of isopropanol.
By the above-mentioned Cu being prepared7S4@MoS2Heterogeneous nanometer framework material is applied to catalytic electrolysis water hydrogen manufacturing.It is specific anti-
Answer condition：The 5wt% perfluorinated sulfonic acid solution of 30ul is added in the dispersion liquid that step b is obtained, wherein 87ul is then taken to be coated in glass
On carbon electrode (electrode diameter 3mm), working electrode is used as after dry, in 0.5M H2SO4In solution, and persistently lead to N2Condition
Under, using glass carbon-point as to electrode, saturation calomel is reference electrode, its linear volt-ampere is tested under the potential condition of 0- ﹣ 0.7v
Curve (LSV), its stability is tested using i-t curves.
Claims (5)
1. a kind of Cu7S4@MoS2The preparation method of heterogeneous nanometer framework material, which is characterized in that it is as follows：
A. 4-6ml oleyl amines and 4-6ml octadecylenes are stirred, then add in the presoma and 20- of the Cu of 0.1-0.5mmol
The presoma of the S of 140mg after 190-210 DEG C keeps 10-20min, continues to be heated to add in 0.2-1mmol at 260-310 DEG C
Mo presoma and 0.4-2mmol S presoma, 275-300 DEG C keep 5-30min；
B. after reacting natural cooling, 5000-15000 revs/min of centrifugation 5-20min of reaction solution is taken out, precipitation is dispersed in n-hexane
In.
2. preparation method according to claim 1, which is characterized in that the presoma of the Cu is selected from copper chloride, acetyl
Acetone copper, copper nitrate.
3. preparation method according to claim 1, which is characterized in that the presoma of the Mo is selected from：Mo(CO)6、Mo
(NO3)3·H2O、MoCl5。
4. preparation method according to claim 1, which is characterized in that the presoma of the S is selected from：Lauryl mercaptan, S
Powder, N, N- dibutyl dithio formic acid.
5. the Cu that preparation method according to claim 1 is prepared7S4@MoS2Heterogeneous nanometer framework material catalytic electrolysis
The application of water hydrogen manufacturing.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107376947A (en) * | 2017-09-21 | 2017-11-24 | 柳州若思纳米材料科技有限公司 | A kind of preparation method of molybdenum disulfide load mangaic acid copper catalyst |
| CN107983371B (en) * | 2017-11-21 | 2020-06-02 | 山东大学 | Photocatalytic material Cu2-xS/Mn0.5Cd0.5S/MoS2And preparation method and application thereof |
| CN107930649A (en) * | 2017-11-30 | 2018-04-20 | 苏州大学 | A kind of base metal oxygen evolution reaction catalysts and preparation method thereof |
| CN109453790A (en) * | 2018-09-17 | 2019-03-12 | 中山大学 | A kind of nanosphere and preparation method thereof of the doped carbon encapsulation transient metal sulfide applied to electro-catalysis |
| CN111389431B (en) * | 2020-05-15 | 2023-01-31 | 郑州大学 | Flake catalyst CoCuPS for hydrogen production by water electrolysis and preparation method thereof |
| CN115029726A (en) * | 2022-06-21 | 2022-09-09 | 上海嘉氢源科技有限公司 | Bimetal FeMoS nano material, preparation method and application |
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| CN103011292A (en) * | 2012-12-04 | 2013-04-03 | 北京大学 | Nolybdenum disulfide nanometer particle, preparation method and application thereof |
| CN103060839A (en) * | 2011-10-20 | 2013-04-24 | 新奥科技发展有限公司 | Low temperature preparation method for hydrogen evolution cathode material and application thereof |
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| CN103060839A (en) * | 2011-10-20 | 2013-04-24 | 新奥科技发展有限公司 | Low temperature preparation method for hydrogen evolution cathode material and application thereof |
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