CN106925301A - A kind of base metal base two dimension MoS2/ Graphene water reducing catalyst with and its preparation method and application - Google Patents
A kind of base metal base two dimension MoS2/ Graphene water reducing catalyst with and its preparation method and application Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 52
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 40
- 229910052961 molybdenite Inorganic materials 0.000 title claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000010953 base metal Substances 0.000 title claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000001257 hydrogen Substances 0.000 claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 37
- 230000001699 photocatalysis Effects 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 238000005286 illumination Methods 0.000 claims description 20
- YIYFFLYGSHJWFF-UHFFFAOYSA-N [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 YIYFFLYGSHJWFF-UHFFFAOYSA-N 0.000 claims description 18
- 230000001235 sensitizing effect Effects 0.000 claims description 18
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 10
- 238000007146 photocatalysis Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 229910015667 MoO4 Inorganic materials 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 238000006722 reduction reaction Methods 0.000 abstract description 10
- 230000009467 reduction Effects 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- 238000004587 chromatography analysis Methods 0.000 description 8
- 239000000470 constituent Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- 229910052724 xenon Inorganic materials 0.000 description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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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
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B01J35/33—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
-
- 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 present invention disclose a kind of base metal base two dimension MoS2/ Graphene water reducing catalysts with and its preparation method and application.The two-dimentional MoS for being developed2/ Graphene can be applied effectively in photo catalytic reduction water prepares hydrogen.Two-dimentional MoS of the invention2/ Graphene water reducing catalyst its chemical general formula is：(MoS2)x(Graphene)y, x:Y is MoS2With the mass ratio of Graphene, x:Y=50 0.25:1.Catalyst of the invention is prepared by hydro-thermal method, using MoS2Excellent proton reduction ability and the good charge transport ability collaboration of Graphene strengthen the performance of its catalytic water reduction hydrogen manufacturing.
Description
Technical field
The invention belongs to clean energy resource transition material field, more particularly, to a kind of two-dimentional MoS2The reduction of/Graphene water is urged
Agent with and its preparation method and application.
Background technology
Energy crisis and two hang-ups that environmental pollution is that the world today faces, development environment is friendly, with low cost, source
Abundant, reproducible green energy resource has become a huge challenge of human social development.Solar energy has aboundresources, divides
Cloth is relatively uniform, without the sorrow point such as transport, environment-friendly, be the optimal energy of future society.Photocatalysis hydrogen production technology is utilized
The abundant solar energy of nature and water resource convert the solar into Hydrogen Energy, are using one of optimal mode of solar energy.
In solar hydrogen making field, the conductor photocatalysis that noble metal is supported have become the photocatalysis hydrogen production material of main flow
Material.In this kind of photochemical catalyst, because noble metal has relatively low fermi level, electronics is easily shifted to noble metal so that expensive
Metal turns into excellent water reducing catalyst.Although especially there is nano platinum particle traditional noble metal catalysis very high to live
Property, but noble metal reserves in the earth are rare, costly, limit their widely using in photocatalysis hydrogen production, this
It is also that photocatalysis hydrogen production system develops the crucial sciences problems of for facing.Design and develop non-precious metal catalyst and urge reducing light
The cost of change system has important Research Significance.
Recent years, with stratiform MoS2It is that the non-platinum catalyst for preparing hydrogen for representing is caused extensively because of its cheap and higher performance
General concern.MoS2It is divided into crystal formation and armorphous two class, their mechanism of action in catalytic water reduction reaction there is also larger
Difference.The molybdenum bisuphide of crystal formation has similar layer structure to Graphene, is combined one by Van der Waals force between layers
Rise.Block crystal formation molybdenum bisuphide is indirect band-gap semiconductor, the reduction potential due to its conduction band positions higher than water, can not
Catalytic water reduction generates hydrogen.Due to quantum size effect, the MoS of nanostructured2Band gap increases as grain diameter is reduced,
Its conduction band potential is reduced also with the reduction of particle diameter, numerically less than water reduction potential.The MoS of crystal formation2Catalytic water reduction
The avtive spot of reaction is located at the exposed unsaturated sulphur atom in Mo (0101) crystal face edge of its lamellar structure.By preparing two dimension
Molybdenum bisuphide superthin section, the more activity edge sites of exposure, are the effective ways for strengthening molybdenum bisuphide catalytic performance.At present
Research on crystal formation molybdenum disulfide catalyst focuses primarily upon the molybdenum disulfide nano sheet for preparing stratiform, and is supported on half
Conductive surface forms the knot of densification, the electric charge transmission between enhancing semiconductor and molybdenum bisuphide, to obtain efficient photocatalysis system
Hydrogen system.Can and, MoS2Electric conductivity it is weak, limit charge transport rate so that pure MoS2With relatively low catalytic performance.
If MoS can be improved2The electric conductivity of base, MoS2Reactivity site will be significantly increased, this to develop it is efficient
Non-precious metal catalyst has important Research Significance.
Based on this, the present invention proposes a kind of by loading Graphene improvement MoS2The active method of base catalyst.This hair
Bright two-dimentional MoS2/ Graphene combines the excellent electric conductivity of Graphene and MoS2Excellent proton reduction ability, is a kind of excellent
, can be applied to photocatalysis water reduce hydrogen manufacturing material.
The content of the invention
First purpose of the invention is directed to existing MoS2The weak deficiency of catalyst electric conductivity, proposes a kind of new non-noble
The MoS of Metal Substrate2/ graphen catalyst.The catalyst has typical two-dimensional layered structure, with larger specific surface and compared with
Electric conductivity high.MoS of the invention2/ graphen catalyst, it is characterised in that the addition of Graphene can be effectively improved
MoS2The electric conductivity and catalytic performance of base catalyst.
The present invention is achieved through the following technical solutions：
A kind of base metal base water reducing catalyst, MoS2Graphenic surface is attached to, is two-dimensional layered structure；Chemistry is logical
Formula is (MoS2)x(Graphene)y, wherein x:Y is MoS in catalyst2With the mass ratio of Graphene, x:Y=50~0.25:1；
Preferably, x：Y=50:1、20:1、10:1、5:1、2:1、1:1、1:2 or 1:4.
Second object of the present invention is to provide a kind of above-mentioned MoS2The preparation method of/graphen catalyst, its feature exists
Prepared by hydro-thermal reaction method at a lower temperature.
The method is specifically with graphene oxide, Na2MoO4It is raw material with thiocarbamide, the matter of requirement is expressed by above-mentioned chemical formula
Amount proportioning is weighed, and is added hydrothermal reaction kettle to heat and be incubated and is allowed to react, and powder sample is obtained after centrifugation, is drying to obtain this
MoS needed for invention2/ graphen catalyst.
According to the present invention, water need to be added as reaction dissolvent.
According to the present invention, before being put into hydrothermal reaction kettle, first by dissolution of raw material is in water and stirs.
According to the present invention, hydrothermal temperature is 150~250 DEG C, and preferably temperature is 200 DEG C, is incubated 24 hours.
Third object of the present invention is to be related to the application of above-mentioned two-dimentional water reducing catalyst.The MoS2/ Graphene is catalyzed
Agent can be used for structure photo catalytic reduction water and prepare hydrogen.
By MoS of the present invention2/ graphen catalyst shines after being combined with commercial zinc porphyrin sensitising agent and triethanolamine in visible ray
Penetrating down can make water be reduced to hydrogen.Wherein every 40 milliliters of MoS2/ graphen catalyst addition 0.05M~0.5M triethanolamines,
50~1000mM zinc porphyrin sensitising agents, preferably 0.2M triethanolamines, 100mM zinc porphyrin sensitising agents；
MoS of the invention2/ graphen catalyst preparation process is simple, with low cost, nontoxic pollution-free, with good
Both thermally and chemically stability and excellent catalysis characteristics, can be applied to structure photo catalytic reduction water and prepare hydrogen.
MoS of the invention2/ graphen catalyst has typical two-dimensional layered structure, with larger specific surface and compared with
Graphene is innovatively added to stratiform crystal formation MoS by electric conductivity high, the especially present invention2, MoS can be effectively improved2Base is catalyzed
The electric conductivity and catalytic performance of agent.
Brief description of the drawings
Fig. 1 is different quality ratio MoS2/ graphen catalyst XRD；
Fig. 2 is MoS2/ Graphene (1:1) scanning electron microscope (SEM) photograph；
Fig. 3 is MoS2/ Graphene (1:1) transmission electron microscope picture；
Fig. 4 is different MoS2Performance of/the graphen catalyst in photocatalysis hydrogen production.
Specific embodiment
Below will by specific embodiment, the present invention will be described in detail, but skilled in the art realises that, Xia Shushi
It is not limiting the scope of the invention to apply example, and any improvement made on the basis of the present invention and change are all of the invention
Within protection domain.
Embodiment 1-1:
Prepare and contain 10mg graphene oxides, 750mg Na2MoO4With 50 milliliters of aqueous solution of 1500mg thiocarbamides, ultrasound it is molten
Added after solution into the polytetrafluoroethylene (PTFE) hydrothermal reaction kettle of 100ml, 24h is reacted at a temperature of 200 DEG C.Question response kettle is cooled to room
Wen Hou, by centrifugation, obtain after solid sample ethanol washes 3 times in an oven 60 DEG C dry 2h, obtain flaxen matter
Amount is than being 50:1 MoS2/ graphene powder sample.
On the basis of embodiment 1-2 to 1-8 is altered to embodiment 1-1 material qualities as shown in table 1, other experiment conditions
It is constant, prepare different quality ratio $MoS2/ graphen catalyst.MoS2The chemical composition of/graphen catalyst passes through
X-ray diffraction (X-Ray Diffraction, XRD) is characterized and confirmed, as shown in Figure 1.By ESEM
(scanning electron microscope, TEM) and transmission electron microscope (Transmission Electron
Microscope, TEM) characterize the shape characteristic of catalyst, as shown in Figures 2 and 3, MoS2/ graphen catalyst has typical case
Two-dimensional layered structure.
Table 1
Embodiment 1-9:
Hydrothermal temperature in embodiment 1 is changed to 150 DEG C, other experiment conditions are prepared into as embodiment 1
Mass ratio to black is 50:1 MoS2/ graphene powder sample.
Embodiment 1-10:
Hydrothermal temperature in embodiment 1 is changed to 250 DEG C, other experiment conditions are prepared into as embodiment 1
Mass ratio to black is 50:1 MoS2/ graphene powder sample.
Embodiment 2-1：
40 milligram 50 is weighed in capacity is for the glass reactor of 350ml:1MoS2/ graphen catalyst, addition contains
The 250ml deionized waters of 0.2M triethanolamines and 100mM zinc porphyrin sensitising agents.By air in solution by vacuumize removal after with
The xenon lamp of 300W is the light source, (λ under visible illumination>420nm) test the performance of photochemical catalyst.The hydrogen that will be generated in system is led
Entering in chromatography of gases carries out constituent analysis.After illumination 4 hours, as shown in figure 4, being based on 50:1MoS2/ Graphene go out hydrogen speed
Rate is 342 μm of olh-1g-1。
Embodiment 2-2：
40 milligram 20 is weighed in capacity is for the glass reactor of 350ml:1MoS2/ graphen catalyst, addition contains
The 250ml deionized waters of 0.2M triethanolamines and 100mM zinc porphyrin sensitising agents.By air in solution by vacuumize removal after with
The xenon lamp of 300W is the light source, (λ under visible illumination>420nm) test the performance of photochemical catalyst.The hydrogen that will be generated in system is led
Entering in chromatography of gases carries out constituent analysis.After illumination 4 hours, based on 20:1MoS2The hydrogen speed that goes out of/Graphene is 730 μ
molh-1g-1.As shown in figure 4, finding 20:1MoS2/ Graphene catalytic performance is 50:1MoS22.1 times of/graphen catalyst.
Embodiment 2-3：
40 milligram 10 is weighed in capacity is for the glass reactor of 350ml:1MoS2/ graphen catalyst, addition contains
The 250ml deionized waters of 0.2M triethanolamines and 100mM zinc porphyrin sensitising agents.By air in solution by vacuumize removal after with
The xenon lamp of 300W is the light source, (λ under visible illumination>420nm) test the performance of photochemical catalyst.The hydrogen that will be generated in system is led
Entering in chromatography of gases carries out constituent analysis.After illumination 4 hours, based on 10:1MoS2The hydrogen speed that goes out of/Graphene is 1942 μ
molh-1g-1.As shown in figure 4, finding 10:1MoS2/ Graphene catalytic performance is 50:1MoS25.7 times of/graphen catalyst.
Embodiment 2-4：
40 milligram 5 is weighed in capacity is for the glass reactor of 350ml:1MoS2/ graphen catalyst, addition contains
The 250ml deionized waters of 0.2M triethanolamines and 100mM zinc porphyrin sensitising agents.By air in solution by vacuumize removal after with
The xenon lamp of 300W is the light source, (λ under visible illumination>420nm) test the performance of photochemical catalyst.The hydrogen that will be generated in system is led
Entering in chromatography of gases carries out constituent analysis.After illumination 4 hours, based on 5:1MoS2The hydrogen speed that goes out of/Graphene is 2486 μ
molh-1g-1.As shown in figure 4, finding 5:1MoS2/ Graphene catalytic performance is 50:1MoS27.3 times of/graphen catalyst.
Embodiment 2-5：
40 milligram 2 is weighed in capacity is for the glass reactor of 350ml:1MoS2/ graphen catalyst, addition contains
The 250ml deionized waters of 0.2M triethanolamines and 100mM zinc porphyrin sensitising agents.By air in solution by vacuumize removal after with
The xenon lamp of 300W is the light source, (λ under visible illumination>420nm) test the performance of photochemical catalyst.The hydrogen that will be generated in system is led
Entering in chromatography of gases carries out constituent analysis.After illumination 4 hours, based on 2:1MoS2The hydrogen speed that goes out of/Graphene is 1574 μ
molh-1g-1.As shown in figure 4, finding 2:1MoS2/ Graphene catalytic performance be 50:1MoS24.6 times of/graphen catalyst.
Embodiment 2-6：
40 milligram 1 is weighed in capacity is for the glass reactor of 350ml:1MoS2/ graphen catalyst, addition contains
The 250ml deionized waters of 0.2M triethanolamines and 100mM zinc porphyrin sensitising agents.By air in solution by vacuumize removal after with
The xenon lamp of 300W is the light source, (λ under visible illumination>420nm) test the performance of photochemical catalyst.The hydrogen that will be generated in system is led
Entering in chromatography of gases carries out constituent analysis.After illumination 4 hours, based on 1:1MoS2The hydrogen speed that goes out of/Graphene is 1234 μ
molh-1g-1.As shown in figure 4, finding 1:1MoS2/ Graphene catalytic performance is 50:1MoS23.6 times of/graphen catalyst.
Embodiment 2-7：
40 milligram 1 is weighed in capacity is for the glass reactor of 350ml:2MoS2/ graphen catalyst, addition contains
The 250ml deionized waters of 0.2M triethanolamines and 100mM zinc porphyrin sensitising agents.By air in solution by vacuumize removal after with
The xenon lamp of 300W is the light source, (λ under visible illumination>420nm) test the performance of photochemical catalyst.The hydrogen that will be generated in system is led
Entering in chromatography of gases carries out constituent analysis.After illumination 4 hours, based on 1:2MoS2The hydrogen speed that goes out of/Graphene is 842 μm of olh-1g-1.As shown in figure 4, finding 1:2MoS2/ Graphene catalytic performance is 50:1MoS22.5 times of/graphen catalyst.
Embodiment 2-8：
40 milligram 1 is weighed in capacity is for the glass reactor of 350ml:4MoS2/ graphen catalyst, addition contains
The 250ml deionized waters of 0.2M triethanolamines and 100mM zinc porphyrin sensitising agents.By air in solution by vacuumize removal after with
The xenon lamp of 300W is the light source, (λ under visible illumination>420nm) test the performance of photochemical catalyst.The hydrogen that will be generated in system is led
Entering in chromatography of gases carries out constituent analysis.After illumination 4 hours, based on 1:4MoS2The hydrogen speed that goes out of/Graphene is 276 μm of olh-1g-1.As shown in figure 4, finding 1:4MoS2/ Graphene catalytic performance is 50:1MoS20.8 times of/graphen catalyst.
Embodiment 2-9:
0.2M triethanolamines in embodiment 2-1 and 100mM zinc porphyrins sensitising agent are changed to 0.05M triethanolamines respectively
With 50mM zinc porphyrin sensitising agents, other experiment conditions as embodiment 2-1, after illumination 4 hours, based on 50:1MoS2/ graphite
The hydrogen speed that goes out of alkene is 342 μm of olh-1g-1。
Embodiment 2-10:
0.2M triethanolamines in embodiment 2-1 and 100mM zinc porphyrins sensitising agent are changed to 0.5M triethanolamines respectively
With 1000mM zinc porphyrin sensitising agents, other experiment conditions as embodiment 2-1, after illumination 4 hours, based on 50:1MoS2/ stone
The hydrogen speed that goes out of black alkene is 1208 μm of olh-1g-1。
Claims (8)
1. a kind of base metal base two dimension MoS2/ Graphene water reducing catalyst, hydrogen can be reduced under visible ray illumination by water
Gas, is two-dimensional layered structure, it is characterised in that the water reducing catalyst chemical general formula is as follows：
(MoS2)x(Graphene)y, wherein x:Y is MoS in catalyst2With the mass ratio of Graphene, x:Y=50~0.25:1.
2. a kind of base metal base two dimension MoS as claimed in claim 12The preparation method of/Graphene water reducing catalyst, should
Preparation method is characterised by that the method is specifically with graphene oxide, Na2MoO4It is reactant with thiocarbamide, by (MoS2)x(stone
Black alkene)yThe mass ratio that chemical formula expression is required is weighed, and heating and insulation reaction in hydrothermal reaction kettle are added after being dissolved in water；
Graphene oxide will be reduced to reduced graphene, Na in hydrothermal reaction process2MoO4Given birth in graphenic surface with thiocarbamide reaction
Into MoS2, the MoS of different quality ratio2/ Graphene water reducing catalyst, can be used after drying.
3. a kind of base metal base two dimension MoS as claimed in claim 22The preparation method of/Graphene water reducing catalyst, its
The heating-up temperature for being characterised by hydro-thermal reaction is 150~250 DEG C.
4. a kind of base metal base two dimension MoS as claimed in claim 32The preparation method of/Graphene water reducing catalyst, its
The heating-up temperature for being characterised by hydro-thermal reaction is 200 DEG C.
5. a kind of base metal base two dimension MoS as claimed in claim 12/ Graphene water reducing catalyst is building photocatalysis also
Application in raw water hydrogen system.
6. application as claimed in claim 5, it is characterised in that will two dimension MoS as claimed in claim 12/ Graphene water is reduced
Catalyst, after being combined with zinc porphyrin sensitising agent and triethanolamine electron donor, hydrogen can be reduced under visible ray illumination by water
Gas.
7. application as claimed in claim 6, it is characterised in that every 40 milliliters of MoS2/ graphen catalyst addition 0.05M~
0.5M triethanolamines, 50~1000mM zinc porphyrin sensitising agents.
8. application as claimed in claim 7, it is characterised in that every 40 milliliters of MoS2/ graphen catalyst adds the second of 0.2M tri-
Hydramine, 100mM zinc porphyrin sensitising agents.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710112030.5A CN106925301A (en) | 2017-02-28 | 2017-02-28 | A kind of base metal base two dimension MoS2/ Graphene water reducing catalyst with and its preparation method and application |
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| CN107335451A (en) * | 2017-07-26 | 2017-11-10 | 河海大学 | The preparation method of platinum/molybdenum disulfide nano sheet/graphene three-dimensional combination electrode catalyst |
| CN108620135A (en) * | 2018-05-17 | 2018-10-09 | 西北师范大学 | A kind of preparation method of molybdenum disulfide composite material |
| CN110252346A (en) * | 2019-05-29 | 2019-09-20 | 江苏大学 | A kind of MoS2/SnS2The preparation method and purposes of/r-GO composite photo-catalyst |
| CN110624572A (en) * | 2019-09-29 | 2019-12-31 | 陕西科技大学 | Flaky semimetal MoTe2And flaky semi-metal MoTe2Preparation method of/RGO |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107335451A (en) * | 2017-07-26 | 2017-11-10 | 河海大学 | The preparation method of platinum/molybdenum disulfide nano sheet/graphene three-dimensional combination electrode catalyst |
| CN107335451B (en) * | 2017-07-26 | 2019-11-26 | 河海大学 | Platinum/molybdenum disulfide nano sheet/graphene three-dimensional combination electrode catalyst preparation method |
| CN108620135A (en) * | 2018-05-17 | 2018-10-09 | 西北师范大学 | A kind of preparation method of molybdenum disulfide composite material |
| CN110252346A (en) * | 2019-05-29 | 2019-09-20 | 江苏大学 | A kind of MoS2/SnS2The preparation method and purposes of/r-GO composite photo-catalyst |
| CN110252346B (en) * | 2019-05-29 | 2022-03-18 | 江苏大学 | MoS2/SnS2Preparation method and application of/r-GO composite photocatalyst |
| CN110624572A (en) * | 2019-09-29 | 2019-12-31 | 陕西科技大学 | Flaky semimetal MoTe2And flaky semi-metal MoTe2Preparation method of/RGO |
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