CN108993542A - The single layer MoS of magnetic atom doping2And its application - Google Patents
The single layer MoS of magnetic atom doping2And its application Download PDFInfo
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- CN108993542A CN108993542A CN201810914289.6A CN201810914289A CN108993542A CN 108993542 A CN108993542 A CN 108993542A CN 201810914289 A CN201810914289 A CN 201810914289A CN 108993542 A CN108993542 A CN 108993542A
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- 239000002356 single layer Substances 0.000 title claims abstract description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 32
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 20
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 20
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 17
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 16
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 16
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000000919 ceramic Substances 0.000 claims description 48
- 239000000758 substrate Substances 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 10
- 238000011144 upstream manufacturing Methods 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 235000014483 powder concentrate Nutrition 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 239000010970 precious metal Substances 0.000 abstract description 6
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 5
- 239000007792 gaseous phase Substances 0.000 abstract description 2
- 125000004429 atom Chemical group 0.000 description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 239000003708 ampul Substances 0.000 description 18
- 239000010453 quartz Substances 0.000 description 18
- 238000002474 experimental method Methods 0.000 description 8
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 7
- -1 because This Substances 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 230000005611 electricity Effects 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000879 optical micrograph Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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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
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- 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
-
- 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
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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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of single layer MoS of magnetic atom doping2, the single layer MoS of the magnetic atom doping2With by AxMoS2The chemical composition that (A=Fe or Co) is indicated.The present invention also provides the single layer MoS of above-mentioned magnetic atom doping2Preparation method, with MoO3Powder, S powder and A2O3(A=Fe or Co) powder is presoma, by simple chemical gaseous phase at method, in SiO2The single layer MoS of large area magnetic atom doping is synthesized on/Si2.The single layer MoS of magnetic atom doping2When catalyst as electrocatalytic decomposition water, excellent electro-catalysis H2-producing capacity is shown.Compared to pure single layer MoS2, catalytic performance has greatly improved, close to precious metals pt.
Description
Technical field
The present invention relates to the single layer MoS that technical field of nano material more particularly to a kind of magnetic atom are adulterated2Preparation side
The application of method and its electro-catalysis H2-producing capacity performance.
Background technique
Environmental pollution caused by non-renewable and its burning of fossil fuel, works as so that exploitation cleaning new energy becomes
The research hotspot of modern academia.Since the heat that combustion of hydrogen is discharged is high, and the product of its burning is free of contamination water, because
This, hydrogen is increasingly subject to the concern of people as a kind of ideal cleaning alternative energy source.Inexpensive, extensive real estate hydrogen is to replace
For one of traditional energy, the important channel for solving current energy crisis.
However currently leads to the problem of hydrogen mode it is many because being faced with due to make hydrogen as energy source development and application be limited.Such as exist
Produce hydrogen it is a series of during, the problems such as having the generation of a large amount of GHG carbon dioxide and cause environmental pollution.Electricity is urged
Changing decomposition water is a kind of clean, sustainable development production hydrogen technology, will be the following weight for solving energy problem and environmental problem
Want one of approach.
During electrolysis water, needs additional electric energy and can effectively destroy the catalyst of hydrone chemical bond.Usually
While generating hydrogen, people always want to it is few as far as possible for the energy of electrochemical reaction, and for decomposing urging for water
Agent has the features such as large specific surface area, durable and catalytic activity is high.Constitute the knot of hydrogen in the atom and water of catalyst
Close the ability that can determine that it promotes electrolysis water reaction: in conjunction with can be too weak, the time of contact on the surface and hydrogen that can make catalyst be too
It is short, to be unfavorable for the progress of scission of link；In conjunction with can catalyst poisoning can be made too by force, to be unfavorable for the further of catalysis reaction
It carries out.
Previous result of study shows that Pt shows very high catalytic efficiency as the catalyst of electrocatalytic decomposition water,
But Pt is a kind of noble metal, reserves on earth are rare, therefore its price is very expensive, and then makes its large-scale application
It is restricted.Therefore, cheap, novel non-noble metal catalyst, alloy, transition such as based on W metal are researched and developed
It metal sulfide, transition metal carbide, transition metal nitride, transition metal boride and some novel nonmetallic urges
Agent is extremely urgent.In recent years, transition metal chalcogenide, such as MoS2, also positive as a kind of novel non-precious metal catalyst
And it is studied extensively by researcher.Currently, it improves with MoS2Hydrogen effect is produced for the electro-catalysis of the transition metal chalcogenide of representative
The approach of rate is mainly improved its catalytic active site dot density and improves its electric conductivity.But raising of these measures to its performance
Still limited, far below the catalytic activity of precious metals pt.
Summary of the invention
Technical problems based on background technology, the present invention are prepared for magnetic atom (Fe by chemical vapour deposition technique
Or Co) doping single layer MoS2, when its catalyst as electrocatalytic decomposition water, show excellent electro-catalysis and produce hydrogen
Energy.
A kind of single layer MoS of magnetic atom doping2, the single layer MoS of the magnetic atom doping2With by AxMoS2It indicates
Chemical composition, A be Fe or Co, the single layer MoS2Area be 0.01-5mm2。
A kind of single layer MoS of magnetic atom doping2Preparation method, method and step is as follows:
S1: S powder is placed in the first ceramic boat, so that S powder concentrates on the first ceramic boat along the upstream end of airflow direction；
And by MoO3And A2O3Mixed-powder be placed in the second ceramic boat, and make MoO3And A2O3Mixed-powder second pottery
The bottom of porcelain boat is equably spread out；
S2: the SiO that will be cleaned2/ Si substrate is placed on the second ceramic boat top, so that the substrate includes SiO2Face
Under；
S3: the first ceramic boat and the second ceramic boat are placed in tube furnace, so that the second ceramic boat is located at the center of furnace,
First ceramic boat is located at air-flow upstream；
S4: the first ceramic boat and the second ceramic boat are calcined under an inert atmosphere, in SiO after cooling2/ Si substrate obtains institute
State the MoS of magnetic atom doping2Sample.
Preferably, the S powder and MoO in the S13The mass ratio of powder is 1:4 to 1:25.
Preferably, the A in the S12O3With MoO3The mass ratio of powder is 1:5 to 1:30.
Preferably, the SiO in the S22/ Si substrate is selected from SiO2(300nm)/Si substrate, SiO2(280nm)/Si substrate
Or SiO2(285nm)/Si substrate.
Preferably, acetone, alcohol are used in the S2 before being calcined, deionized water is cleaned by ultrasonic SiO respectively2/ Si substrate.
Preferably, the alcohol is selected from dehydrated alcohol, propyl alcohol or isopropanol.
Preferably, the calcination temperature in the S4 is 550-1000 DEG C, and the heating rate in calcining in the S4 is 10-
30 DEG C/min, the soaking time in calcining is 5-15min.
Preferably, inert atmosphere described in the S4 is selected from nitrogen, helium, neon, argon gas, Krypton and xenon etc., described
The air-flow size of inert atmosphere is 10sccm to 100sccm.
A kind of single layer MoS of magnetic atom doping proposed by the present invention2Hydrogen catalyst is produced applied to electro-catalysis.
Action principle:
For MoS2For, active site is predominantly located at the boundary of layer structure, and its boundary mainly byThe boundary S andThe boundary Mo is constituted.The catalytic activity of boundary mainly byThe contribution of the boundary Mo, andThe boundary S does not have catalytic activity, and two kinds of border structures respectively account for half.The incorporation of magnetic atom Co or Fe can activate
Boundary does not have catalytic activityThe boundary S makes it have catalytic activity as the boundary Mo, so that entire boundary
All have catalytic activity.At the same time, the incorporation of magnetic atom Co or Fe can also change the periodical knot of atomic arrangement in plane
Structure and its electronic band structure, so that the atom in plane also has catalytic activity.That is magnetic atom Co's or Fe mixes
Enter the inert atom that can be activated in the boundary inertia S and plane, to greatly improve MoS2Electro-catalysis produce hydrogen activity.
Compared with prior art, the device have the advantages that being:
The atom doped single layer MoS of one-dimensional magnetic proposed by the present invention2, the single layer MoS of the magnetic atom doping2Have
By AxMoS2The chemical composition that (A=Fe or Co) is indicated.The present invention also provides the single layer MoS of above-mentioned magnetic atom doping2System
Preparation Method, with MoO3Powder, S powder and A2O3(A=Fe or Co) powder is presoma, by simple chemical gaseous phase at method,
SiO2The single layer MoS of large area magnetic atom doping is synthesized on/Si2.The single layer MoS of magnetic atom doping2As electrocatalytic decomposition
When the catalyst of water, excellent electro-catalysis H2-producing capacity is shown.Compared to pure single layer MoS2, catalytic performance has very big mention
It rises, cut-in voltage reaches -200mV, and Tafel is down to 45mV/dec, close to precious metals pt.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the atom doped single layer MoS of Co that embodiment 1 synthesizes2Optical microscope picture；
Fig. 2 is the atom doped single layer MoS of Co that embodiment 1 synthesizes2Atomic force microscope images；
Fig. 3 is the atom doped single layer MoS of Co that embodiment 1 synthesizes2The EDS energy spectrum diagram of sample；
Fig. 4 is the atom doped single layer MoS of Co that embodiment 1 synthesizes2Electro-catalysis produce hydrogen polarization curve graph；
Fig. 5 is the atom doped single layer MoS of Co that embodiment 1 synthesizes2Electro-catalysis produce hydrogen Tafel figure；
Fig. 6 is the single layer MoS of comparative experiments preparation synthesis2Electro-catalysis produce hydrogen polarization curve graph；
Fig. 7 is the single layer MoS of comparative experiments preparation synthesis2Electro-catalysis produce hydrogen Tafel figure.
Specific embodiment
Combined with specific embodiments below the present invention is made further to explain.
Embodiment 1
S1: S powder is placed in the first ceramic boat, so that S powder concentrates on the first ceramic boat along the upstream end of airflow direction；
And by MoO3And Co2O3Mixed-powder be placed in the second ceramic boat, and make MoO3And Co2O3Mixed-powder second
The bottom of ceramic boat is equably spread out；S powder and MoO3The mass ratio of powder is 1:3, the Co in S12O3With MoO3The quality of powder
Than for 1:30.
S2: it is cleaned by ultrasonic SiO respectively with acetone, dehydrated alcohol, deionized water2(300nm)/Si substrate 10min；It will cleaning
The SiO crossed2(300nm)/Si substrate is placed on the second ceramic boat top, so that substrate includes SiO2It is face-down；
S3: two ceramic boats are placed in the quartz ampoule of tube furnace, wherein hold Co2O3And MoO3The ceramic boat of powder is put
In the center of quartz ampoule, the boat for holding S powder is placed on the upstream of air-flow, and the central 11cm apart from quartz ampoule.Closed good quartz ampoule
Afterwards, the inner air of quartz ampoule is drained with vacuum pump and high-purity Ar gas, and made in pipe for high-purity Ar compression ring border；With 15 DEG C/min
Heating rate quartz ampoule is heated to 650 DEG C from room temperature, in 650 DEG C of heat preservation 5min, entire stove is then allowed to naturally cool to
Room temperature.It is 50sccm that whole experiment process, which keeps the air-flow size of high-purity Ar gas,.
S4: the first ceramic boat and the second ceramic boat are calcined under an inert atmosphere, in SiO after cooling2/ Si substrate obtains institute
State the MoS of magnetic atom doping2Sample.
Sample made from embodiment 1 is detected: with Nikon optical microphotograph sem observation, as shown in pattern attached drawing 1, film
Area is up to 0.06mm2；Its thickness is measured with atomic force microscope, it is found that its thickness is about 0.9nm, as shown in Fig. 2, explanation
Synthesized large area film Co adulterates MoS2For single layer.In order to confirm that Co atom is successfully embed into MoS2Lattice in, to it
Power spectrum test is carried out, as shown in Fig. 3, as can be seen from the figure Co atom is successfully embed into single layer MoS2In.
The Co being prepared is adulterated into single layer MoS2Catalyst as electrocatalytic decomposition water, experiment are based on three electrodes
Electrochemical workstation (660E CH, Shanghai Hua Chen equipment Co., Ltd) on complete.In these three electrodes, it is loaded with sample
GCE as working electrode, Ag/AgCl (3M KCl) is used as reference electrode, and carbon-point is used as to electrode.Electrochemical catalysis when experiment
Electrolyte used in testing is the H that concentration is 0.5mol/L2SO4Solution.The sweep speed of the linear sweep voltammetry carried out
For 5mV/s, scanning range is 0.2V to -0.75V.Attached drawing 4 and attached drawing 5 respectively show the atom doped single layer MoS of Co2As electricity
Catalysis produces the polarization curve and Tafel curve when hydrogen catalyst, there it can be seen that the atom doped single layer MoS of Co2Sample performance
Excellent electrocatalysis characteristic is gone out, cut-in voltage reaches -200mV, and Tafel is down to 45mV/dec, close to excellent electricity
The precious metals pt of catalytic performance (the Tafel slope of Pt is~36mV/dec).
Embodiment 2
S1: S powder is placed in the first ceramic boat, so that S powder concentrates on the first ceramic boat along the upstream end of airflow direction；
And by MoO3And Co2O3Mixed-powder be placed in the second ceramic boat, and make MoO3And Co2O3Mixed-powder second
The bottom of ceramic boat is equably spread out；S powder and MoO3The mass ratio of powder is 1:4, Co2O3With MoO3The mass ratio of powder is 1:
5。
S2: it is cleaned by ultrasonic SiO respectively with acetone, propyl alcohol, deionized water2(280nm)/Si substrate 10min；By what is cleaned
SiO2(280nm)/Si substrate is placed on the second ceramic boat top, so that substrate includes SiO2It is face-down；
S3: two ceramic boats are placed in the quartz ampoule of tube furnace, wherein hold Co2O3And MoO3The ceramic boat of powder is put
In the center of quartz ampoule, the boat for holding S powder is placed on the upstream of air-flow, and the central 11cm apart from quartz ampoule.Closed good quartz ampoule
Afterwards, the inner air of quartz ampoule is drained with vacuum pump and high pure nitrogen, and made in pipe for high pure nitrogen environment；With 10 DEG C/min
Heating rate quartz ampoule is heated to 550 DEG C from room temperature, in 550 DEG C of heat preservation 10min, entire stove is then allowed to naturally cool to
Room temperature.It is 10sccm that whole experiment process, which keeps the air-flow size of high pure nitrogen,.
S4: the first ceramic boat and the second ceramic boat are calcined under an inert atmosphere, in SiO after cooling2/ Si substrate obtains institute
State the MoS of magnetic atom doping2Sample.
Detect to sample made from embodiment 2: with Nikon optical microphotograph sem observation, the area of film is up to 0.05mm2；
Its thickness is measured with atomic force microscope, it is found that its thickness is about 0.8nm.
Embodiment 3
S1: S powder is placed in the first ceramic boat, so that S powder concentrates on the first ceramic boat along the upstream end of airflow direction；
And by MoO3And Fe2O3Mixed-powder be placed in the second ceramic boat, and make MoO3And Fe2O3Mixed-powder second
The bottom of ceramic boat is equably spread out；S powder and MoO3The mass ratio of powder be 1:25, Fe2O3With MoO3The mass ratio of powder is
1:25。
S2: it is cleaned by ultrasonic SiO respectively with acetone, isopropanol, deionized water2(285nm)/Si substrate 10min；It will clean
SiO2(285nm)/Si substrate is placed on the second ceramic boat top, so that substrate includes SiO2It is face-down；
S3: two ceramic boats are placed in the quartz ampoule of tube furnace, wherein hold Fe2O3And MoO3The ceramic boat of powder is put
In the center of quartz ampoule, the boat for holding S powder is placed on the upstream of air-flow, and the central 11cm apart from quartz ampoule.Closed good quartz ampoule
Afterwards, the inner air of quartz ampoule is drained with vacuum pump and high-purity helium, and made in pipe for high-purity helium environment；With 30 DEG C/min
Heating rate quartz ampoule is heated to 1000 DEG C from room temperature, in 1000 DEG C of heat preservation 15min, then allow entire stove natural cooling
To room temperature.It is 100sccm that whole experiment process, which keeps the air-flow size of high-purity helium,.
S4: the first ceramic boat and the second ceramic boat are calcined under an inert atmosphere, in SiO after cooling2/ Si substrate obtains institute
State the MoS of magnetic atom doping2Sample.
Detect to sample made from embodiment 3: with Nikon optical microphotograph sem observation, the area of film is up to 5mm2；With
Atomic force microscope measures its thickness, it is found that its thickness is about 0.7nm.
Comparative test
During entire synthesis, presoma only chooses S powder and MoO3Powder, using with the identical experiment of embodiment 1
Condition has successfully synthesized single layer MoS2Sample.Single layer MoS2The polarization curve and Tafel song of hydrogen catalyst are produced as electro-catalysis
Line is as shown in attached drawing 6 and attached drawing 7.It can be seen from the figure that its cut-in voltage is -340mV, Tafel 85mV/dec.
Compared to pure single layer MoS2, the MoS of Co doping2With higher cut-in voltage and lower Tafel slope, and
The MoS of Co doping2Catalytic performance close to precious metals pt, therefore the MoS of magnetic atom doping that this patent is related to2It is urged in electricity
Changing has extraordinary application prospect in terms of producing hydrogen.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of single layer MoS of magnetic atom doping2, which is characterized in that the single layer MoS of the magnetic atom doping2With by
AxMoS2The chemical composition of expression, A are Fe or Co, the single layer MoS2Area be 0.01-5mm2。
2. a kind of single layer MoS of magnetic atom doping according to claim 12Preparation method, which is characterized in that method
Steps are as follows:
S1: S powder is placed in the first ceramic boat, so that S powder concentrates on the first ceramic boat along the upstream end of airflow direction；And
By MoO3And A2O3Mixed-powder be placed in the second ceramic boat, and make MoO3And A2O3Mixed-powder in the second ceramic boat
Bottom equably spread out；
S2: the SiO that will be cleaned2/ Si substrate is placed on the second ceramic boat top, so that the substrate includes SiO2It is face-down；
S3: the first ceramic boat and the second ceramic boat are placed in tube furnace, so that the second ceramic boat is located at the center of furnace, first
Ceramic boat is located at air-flow upstream；
S4: the first ceramic boat and the second ceramic boat are calcined under an inert atmosphere, obtain the magnetic in SiO2/Si substrate after cooling
The atom doped MoS of property2Sample.
3. a kind of single layer MoS of magnetic atom doping according to claim 22Preparation method, which is characterized in that it is described
S powder and MoO in S13The mass ratio of powder is 1:4 to 1:25.
4. a kind of single layer MoS of magnetic atom doping according to claim 22Preparation method, which is characterized in that it is described
A in S12O3With MoO3The mass ratio of powder is 1:5 to 1:30.
5. a kind of single layer MoS of magnetic atom doping according to claim 22Preparation method, which is characterized in that it is described
SiO in S22/ Si substrate is selected from SiO2(300nm)/Si substrate, SiO2(280nm)/Si substrate or SiO2(285nm)/Si lining
Bottom.
6. a kind of single layer MoS of magnetic atom doping according to claim 22Preparation method, which is characterized in that it is described
Acetone, alcohol are used in S2 before being calcined, deionized water is cleaned by ultrasonic SiO respectively2/ Si substrate.
7. a kind of single layer MoS of magnetic atom doping according to claim 62Preparation method, which is characterized in that it is described
Alcohol is selected from dehydrated alcohol, propyl alcohol or isopropanol.
8. a kind of single layer MoS of magnetic atom doping according to claim 22Preparation method, which is characterized in that it is described
Calcination temperature in S4 is 550-1000 DEG C, and the heating rate in calcining in the S4 is 10-30 DEG C/min, the guarantor in calcining
The warm time is 5-15min.
9. a kind of single layer MoS of magnetic atom doping according to claim 22Preparation method, which is characterized in that it is described
Inert atmosphere described in S4 is selected from nitrogen, helium, neon, argon gas, Krypton and xenon etc., and the air-flow size of the inert atmosphere is
10sccm to 100sccm.
10. a kind of described in any item single layer MoS of magnetic atom doping of claim 1-92Hydrogen catalysis is produced applied to electro-catalysis
Agent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111218717A (en) * | 2020-02-17 | 2020-06-02 | 燕山大学 | Growing Fe-doped single-layer WS2Method for two-dimensional crystallization |
| CN113617369A (en) * | 2020-05-07 | 2021-11-09 | 中国石油天然气股份有限公司 | Magnetic-carrier catalyst for modifying inferior heavy oil and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622296A (en) * | 2016-10-12 | 2017-05-10 | 吉林大学 | MoS2/CoS2 composite water-splitting hydrogen-production low-overpotential electrocatalyst and sulfidation preparation method thereof |
| CN107262117A (en) * | 2017-07-25 | 2017-10-20 | 华中师范大学 | The method of the few layer molybdenum disulfide electrocatalysis material of monoatomic metal doping, synthesis and its electro-catalysis fixed nitrogen |
| CN108385132A (en) * | 2018-03-09 | 2018-08-10 | 三峡大学 | A kind of Co doping MoS2The CVD preparation methods of array original position electrode |
-
2018
- 2018-08-13 CN CN201810914289.6A patent/CN108993542A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622296A (en) * | 2016-10-12 | 2017-05-10 | 吉林大学 | MoS2/CoS2 composite water-splitting hydrogen-production low-overpotential electrocatalyst and sulfidation preparation method thereof |
| CN107262117A (en) * | 2017-07-25 | 2017-10-20 | 华中师范大学 | The method of the few layer molybdenum disulfide electrocatalysis material of monoatomic metal doping, synthesis and its electro-catalysis fixed nitrogen |
| CN108385132A (en) * | 2018-03-09 | 2018-08-10 | 三峡大学 | A kind of Co doping MoS2The CVD preparation methods of array original position electrode |
Non-Patent Citations (1)
| Title |
|---|
| LEI YANG, ET AL.: "Single-crystal atomic-layered molybdenum disulfide nanobelts with high surface activity", 《ACS NANO》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111218717A (en) * | 2020-02-17 | 2020-06-02 | 燕山大学 | Growing Fe-doped single-layer WS2Method for two-dimensional crystallization |
| CN113617369A (en) * | 2020-05-07 | 2021-11-09 | 中国石油天然气股份有限公司 | Magnetic-carrier catalyst for modifying inferior heavy oil and preparation method and application thereof |
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