CN109482200A - Porous carbon-supported defect molybdenum sulfide elctro-catalyst of one kind and preparation method thereof - Google Patents
Porous carbon-supported defect molybdenum sulfide elctro-catalyst of one kind and preparation method thereof Download PDFInfo
- Publication number
- CN109482200A CN109482200A CN201811382910.5A CN201811382910A CN109482200A CN 109482200 A CN109482200 A CN 109482200A CN 201811382910 A CN201811382910 A CN 201811382910A CN 109482200 A CN109482200 A CN 109482200A
- Authority
- CN
- China
- Prior art keywords
- porous carbon
- molybdenum sulfide
- supported
- preparation
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 230000007547 defect Effects 0.000 title claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 24
- 238000003763 carbonization Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000009413 insulation Methods 0.000 claims abstract description 14
- 238000010792 warming Methods 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000002772 monosaccharides Chemical class 0.000 claims abstract description 11
- 229960001553 phloroglucinol Drugs 0.000 claims abstract description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 10
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 10
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 10
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims abstract description 4
- 239000012046 mixed solvent Substances 0.000 claims abstract description 4
- 238000012545 processing Methods 0.000 claims abstract description 4
- 229910052786 argon Inorganic materials 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 9
- PYMYPHUHKUWMLA-VPENINKCSA-N aldehydo-D-xylose Chemical compound OC[C@@H](O)[C@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-VPENINKCSA-N 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229930091371 Fructose Natural products 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims 1
- 238000005470 impregnation Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000004146 energy storage Methods 0.000 abstract description 2
- 239000011232 storage material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 13
- 229910052750 molybdenum Inorganic materials 0.000 description 13
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 13
- 229910052961 molybdenite Inorganic materials 0.000 description 12
- 239000011733 molybdenum Substances 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 239000003575 carbonaceous material Substances 0.000 description 9
- 239000005864 Sulphur Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to be catalyzed with energy storage material field, disclose a kind of porous carbon-supported defect molybdenum sulfide elctro-catalyst and preparation method thereof.Monosaccharide and phloroglucin are reacted in alcohol water mixed solvent with graphene oxide, product is freeze-dried, then carbonization treatment at a temperature of 700~900 DEG C, and the processing of concentrated nitric acid hot submersion obtains functionalization porous carbon；Ammonium molybdate and thiocarbamide and functionalization porous carbon are warming up to 180~240 DEG C of insulation reactions in water, obtain porous carbon-supported molybdenum sulfide；Porous carbon-supported molybdenum sulfide is mixed with red phosphorus, then the carbonization treatment at a temperature of mixed atmosphere of hydrogen and argon gas and 600~900 DEG C, obtains porous carbon-supported defect molybdenum sulfide elctro-catalyst.Preparation method of the present invention is raw materials used cheap and easy to get, MoS in products therefrom2Petal-shaped vertical-growth is presented in porous carbon substrate in nanometer sheet, has more edge active sites, and catalytic activity is high.
Description
Technical field
The invention belongs to be catalyzed and energy storage material field, and in particular to a kind of porous carbon-supported defect molybdenum sulfide electro-catalysis
Agent and preparation method thereof.
Background technique
The raising of industrial expansion and human living standard be unable to do without the consumption of the energy.Since the consumption of traditional energy generates
More oxycarbide, nitrogen oxides and acid rain etc. cause seriously to pollute to environment.It is dirty in order to solve energy crisis and environment
The problems such as dye, develops and utilizes environmentally friendly, cleaning, inexpensive, renewable energy system gradually causes people widely to pay close attention to.Oxygen
Reduction reaction and evolving hydrogen reaction play a key role in fields such as fuel cell, zinc and air cell and anti-corrosion protections.So far,
Noble metal-based catalysts, including Pt, Pd, Ru and their alloy, due to its take-off potential is low and Tafel slope is small and by
It is widely used as ORR and HER reaction.However, its disadvantages of there are at high cost, reserves are low and low mithridatism, hinder noble metal and urge
The extensive use of agent.Therefore, exploitation have high activity, good stability and cheap base metal base elctro-catalyst for
The development of water electrolysis hydrogen production be there is an urgent need to.
Currently, have a large amount of research work and concentrate on to develop and the non-of good electrocatalysis characteristic is shown to HER or ORR
Noble metal-based catalysts, wherein the research of transition metal element base catalyst is relatively broad and mature, mainly there is phosphide, carbonization
Object, selenides, nitride and sulfide.MoS2Due to having been widely used for unique electronics, chemical and physical features
The fields such as supercapacitor, lithium ion battery, water electrolysis hydrogen production.As typical Transition-metal dichalcogenide, MoS2Be according to
Three stacking atomic layers (S-Mo-S) composition to link together by Van der Waals force.The molybdenum disulfide of single layer is a kind of similar Sanming City
The interlayer structure controlled, upper layer and lower layer are sulphur atoms, and one layer for being added in position among them is then molybdenum atom.Each layer of thickness is about
For 0.7nm, spacing between layers isMoS2Crystal structure mainly include 1T-MoS2(square is symmetrical),
2H-MoS2(hexagonal symmetry) and 3R-MoS2(oblique six aspects body is symmetrical).Experiment and calculated result show MoS2Liberation of hydrogen catalysis
Active site is mainly derived from the edge of sulphur, and basal plane is inert.Further, since in the presence of more exposed active site, institute
With the MoS of nano-scale2It should be more active than figure.Therefore, design has the MoS in more edge sites2It is to improve MoS2Base
One of active possible strategy of elctro-catalyst.High conductivity may insure the fast transfer of electronics in catalytic process, to catalyst
Catalytic activity it is most important.MoS2Since band gap is larger, poor conductivity is shown, can obviously limit the speed of evolving hydrogen reaction
Rate.
Carbonaceous material, such as carbon nanotube, carbon fiber, porous carbon, carbon ball, carbon nanosheet and graphene, due to having height
Electron conduction, low-density, low cost and the advantages such as porous structure are readily synthesized, it not only can be directly as water electrolysis hydrogen production
Catalyst, and be also widely used for preparing the excellent carrier of hybrid catalyst.It can be with other noble metals or cheap
Metal carry out it is compound, be capable of forming the catalyst of high catalytic activity.Although and MoS2Compound carbonaceous material has been developed that simultaneously
Applied to electrochemical catalysis, but exposing more active sites simultaneously and improving stability is still a significant challenge.
Summary of the invention
In place of the above shortcoming and defect of the existing technology, the primary purpose of the present invention is that providing a kind of porous
The preparation method of the molybdenum sulfide elctro-catalyst of carbon-supported defect.
Another object of the present invention is to provide a kind of porous carbon-supported defects being prepared by the above method
Molybdenum sulfide elctro-catalyst.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of the molybdenum sulfide elctro-catalyst of porous carbon-supported defect, including following preparation step:
(1) preparation of functionalization porous carbon: under magnetic stirring, monosaccharide and phloroglucin is dissolved in and is made of alcohol and water
In the mixed solvent, then addition graphene oxide (GO) ultrasonic disperse is uniform, is warming up to 150~200 DEG C of insulation reactions, and solid produces
Object is washed, then freeze-drying carries out carbonization treatment, products therefrom is through dense nitre at a temperature of inert atmosphere and 700~900 DEG C
Sour hot submersion processing, obtains functionalization porous carbon；
(2) preparation of porous carbon-supported molybdenum sulfide: ammonium molybdate and thiocarbamide are dissolved in the water, and step (1) institute is then added
Functionalization porous carbon is obtained, ultrasonic treatment forms uniform suspension, then heats to 180~240 DEG C of insulation reactions, obtain porous
Carbon-supported molybdenum sulfide；
(3) preparation of porous carbon-supported defect molybdenum sulfide: porous carbon-supported molybdenum sulfide is mixed with red phosphorus, then in hydrogen
Mixing (the Ar/H of gas and argon gas2) carbonization treatment at a temperature of atmosphere and 600~900 DEG C, obtain porous carbon-supported defectization vulcanization
Molybdenum elctro-catalyst.
Preferably, monosaccharide described in step (1) refers to one of D- xylose, glucose, fructose or two or more
Mixing.
Preferably, the mass ratio that monosaccharide described in step (1) and phloroglucin are added is (1~3): 1.
Preferably, the in the mixed solvent of the composition of alcohol and water described in step (1), the volume ratio of alcohol and water are 1:(1~3).
Preferably, the time of insulation reaction described in step (1) be 12~for 24 hours, time of carbonization treatment is 2~5h.
Preferably, the temperature of the processing of concentrated nitric acid hot submersion described in step (1) is 90~120 DEG C, and the time is 1~3h.
Preferably, the ratio between the amount of substance that ammonium molybdate described in step (2) and thiocarbamide are added is (0.1~0.5): (1~
10)。
Preferably, the time of insulation reaction described in step (2) be 20~for 24 hours.
Preferably, the mass ratio that porous carbon-supported molybdenum sulfide is mixed with red phosphorus described in step (3) is 1:(1~10).
Preferably, the time of carbonization treatment described in step (3) is 1~5h.
A kind of molybdenum sulfide elctro-catalyst of porous carbon-supported defect, is prepared by the above method.
Preparation principle of the invention are as follows:
Under conditions of hydro-thermal, graphene oxide, monosaccharide and phloroglucin form hydrogel by way of self assembly, warp
The mode for crossing freeze-drying and carbonization treatment obtains porous carbon materials.By the acidification of concentrated nitric acid, so that porous carbon surface
Rich in oxygen-containing functional group, and then change the hydrophilic and hydrophobic at its interface.Then, molybdenum sulfide and porous carbon are prepared by means of hydrothermal synthesis
Hybrid.Finally, red phosphorus to be introduced to the hybrid of molybdenum sulfide and porous carbon, during high temperature reduction, phosphorus atoms replace
Sulphur atom in molybdenum sulfide in turn results in the defect of molybdenum sulfide.
Preparation method of the invention and obtained product have the following advantages that and the utility model has the advantages that
(1) present invention utilizes the self assembly of monosaccharide and phloroglucin cheap and easy to get to prepare for the life as conductive carrier
Substance base carbon material, then the porous carbon-supported defect molybdenum sulfide of monosaccharide groups is prepared for by one step hydro thermal method and carbothermic method
Elctro-catalyst.On the basis of rationally utilizing biomass resource, a kind of new approaches are provided for the development of subsequent elctro-catalyst.
(2) molybdenum sulfide nanometer sheet vertical arrangement is grown on monosaccharide groups porous carbon support in products therefrom of the present invention, not only
Be conducive to expose more edge active sites, promote the raising of catalyst activity, and is advantageously implemented lacking for later period
Sunkenization.
Detailed description of the invention
Fig. 1 is gained functionalization porous carbon (a, b) and the middle porous carbon-supported sulphur of gained of step (2) in 5 step of embodiment (1)
Change scanning electron microscope (SEM) figure of molybdenum (c, d).
Fig. 2 is porous carbon-supported scarce for gained in the porous carbon-supported molybdenum sulfide of gained in 5 step of embodiment (2) and step (3)
X-ray diffraction (XRD) spectrogram of sunkenization molybdenum sulfide.
Fig. 3 is porous carbon-supported defect molybdenum sulfide (1:10) and existing palladium-carbon catalyst (20% prepared by embodiment 5
Pt/C) in the polarization curve of 0.5M sulphuric acid electrolyte water hydrogen manufacturing.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
The preparation method of the porous carbon-supported defect molybdenum sulfide elctro-catalyst of one kind of the present embodiment, specific preparation step is such as
Under:
(1) preparation of functionalization porous carbon: under magnetic stirring, 0.1g D- xylose and 0.1g phloroglucin are dissolved in
In the mixed solution that 10mL is made of alcohol and water (volume ratio of alcohol to water 1:2).Then, 5mL1mmol/L GO is slowly added into
In solution and by being ultrasonically treated evenly dispersed 0.5h.Then, mixture solution is transferred to 50mL polytetrafluoroethylsubstrate substrate
180 DEG C of heating reaction 16h are warming up in autoclave.Solid product is washed with water and is lyophilized, and obtains porous carbon materials.In nitrogen atmosphere
Under, porous carbon is heated into 2h in 700 DEG C of tube furnaces.Then the porous carbon after carbonization is further added at 90 DEG C with concentrated nitric acid
Hot submersion handles 1h, and products therefrom is functionalization porous carbon.
(2) preparation of porous carbon-supported molybdenum sulfide: 0.2mmol ammonium molybdate and 1mmol thiocarbamide are dissolved in 35mL water, stirred
It mixes uniformly, 0.05g functionalization porous carbon is added in Xiang Shangshu solution, ultrasonic treatment 30min forms uniform suspension.It will suspend
Liquid is transferred in the autoclave of 50mL polytetrafluoroethylsubstrate substrate and is warming up to 200 DEG C of insulation reactions for 24 hours, obtains porous carbon-supported sulphur
Change molybdenum.
(3) preparation of porous carbon-supported defect molybdenum sulfide: by porous carbon-supported material molybdenum sulfide and red phosphorus (mass ratio
Example, 1:1) it ground, mixed, mixture is in Ar/H2600 DEG C of carbonization 1h in atmosphere obtain porous carbon-supported defectization vulcanization
Molybdenum elctro-catalyst.
Embodiment 2
The preparation method of the porous carbon-supported defect molybdenum sulfide elctro-catalyst of one kind of the present embodiment, specific preparation step is such as
Under:
(1) preparation of functionalization porous carbon: under magnetic stirring, 0.5g D- xylose and 0.2g phloroglucin are dissolved in
In the mixed solution that 10mL is made of alcohol and water (volume ratio of alcohol to water 1:1).Then, 5mL1mmol/L GO is slowly added into
In solution and by being ultrasonically treated evenly dispersed 0.5h.Then, mixture solution is transferred to 50mL polytetrafluoroethylsubstrate substrate
180 DEG C of heating reaction 16h are warming up in autoclave.Solid product is washed with water and is lyophilized, and obtains porous carbon materials.In nitrogen atmosphere
Under, porous carbon is heated into 2h in 800 DEG C of tube furnaces.Then the porous carbon after carbonization is further added at 90 DEG C with concentrated nitric acid
Hot submersion handles 1h, and products therefrom is functionalization porous carbon.
(2) preparation of porous carbon-supported molybdenum sulfide: 0.5mmol ammonium molybdate and 1mmol thiocarbamide are dissolved in 35mL water, stirred
It mixes uniformly, 0.05g functionalization porous carbon is added in Xiang Shangshu solution, ultrasonic treatment 30min forms uniform suspension.It will suspend
Liquid is transferred in the autoclave of 50mL polytetrafluoroethylsubstrate substrate and is warming up to 200 DEG C of insulation reactions for 24 hours, obtains porous carbon-supported sulphur
Change molybdenum.
(3) preparation of porous carbon-supported defect molybdenum sulfide: by porous carbon-supported material molybdenum sulfide and red phosphorus (mass ratio
Example, 1:1) it ground, mixed, mixture is in Ar/H2700 DEG C of carbonization 1h in atmosphere obtain porous carbon-supported defectization vulcanization
Molybdenum elctro-catalyst.
Embodiment 3
The preparation method of the porous carbon-supported defect molybdenum sulfide elctro-catalyst of one kind of the present embodiment, specific preparation step is such as
Under:
(1) preparation of functionalization porous carbon: under magnetic stirring, 0.89g D- xylose and 0.31g phloroglucin are dissolved in
In the mixed solution that 10mL is made of alcohol and water (volume ratio of alcohol to water 1:3).Then, 5mL1mmol/L GO is slowly added into
In solution and by being ultrasonically treated evenly dispersed 0.5h.Then, mixture solution is transferred to 50mL polytetrafluoroethylsubstrate substrate
180 DEG C of heating reaction 16h are warming up in autoclave.Solid product is washed with water and is lyophilized, and obtains porous carbon materials.In nitrogen atmosphere
Under, porous carbon is heated into 2h in 800 DEG C of tube furnaces.Then the porous carbon after carbonization is further added at 90 DEG C with concentrated nitric acid
Hot submersion handles 1h, and products therefrom is functionalization porous carbon.
(2) preparation of porous carbon-supported molybdenum sulfide: 0.2mmol ammonium molybdate and 6mmol thiocarbamide are dissolved in 35mL water, stirred
It mixes uniformly, 0.05g functionalization porous carbon is added in Xiang Shangshu solution, ultrasonic treatment 30min forms uniform suspension.It will suspend
Liquid is transferred in the autoclave of 50mL polytetrafluoroethylsubstrate substrate and is warming up to 200 DEG C of insulation reactions for 24 hours, obtains porous carbon-supported sulphur
Change molybdenum.
(3) preparation of porous carbon-supported defect molybdenum sulfide: by porous carbon-supported material molybdenum sulfide and red phosphorus (mass ratio
Example, 1:1) it ground, mixed, mixture is in Ar/H2750 DEG C of carbonization 1h in atmosphere obtain porous carbon-supported defectization vulcanization
Molybdenum elctro-catalyst.
Embodiment 4
The preparation method of the porous carbon-supported defect molybdenum sulfide elctro-catalyst of one kind of the present embodiment, specific preparation step is such as
Under:
(1) preparation of functionalization porous carbon: under magnetic stirring, 0.89g D- xylose and 0.31g phloroglucin are dissolved in
In the mixed solution that 10mL is made of alcohol and water (volume ratio of alcohol to water 1:2).Then, 5mL1mmol/L GO is slowly added into
In solution and by being ultrasonically treated evenly dispersed 0.5h.Then, mixture solution is transferred to 50mL polytetrafluoroethylsubstrate substrate
180 DEG C of heating reaction 16h are warming up in autoclave.Solid product is washed with water and is lyophilized, and obtains porous carbon materials.In nitrogen atmosphere
Under, porous carbon is heated into 2h in 800 DEG C of tube furnaces.Then the porous carbon after carbonization is further added at 90 DEG C with concentrated nitric acid
Hot submersion handles 1h, and products therefrom is functionalization porous carbon.
(2) preparation of porous carbon-supported molybdenum sulfide: 0.2mmol ammonium molybdate and 6mmol thiocarbamide are dissolved in 35mL water, stirred
It mixes uniformly, 0.05g functionalization porous carbon is added in Xiang Shangshu solution, ultrasonic treatment 30min forms uniform suspension.It will suspend
Liquid is transferred in the autoclave of 50mL polytetrafluoroethylsubstrate substrate and is warming up to 200 DEG C of insulation reactions for 24 hours, obtains porous carbon-supported sulphur
Change molybdenum.
(3) preparation of porous carbon-supported defect molybdenum sulfide: by porous carbon-supported material molybdenum sulfide and red phosphorus (mass ratio
Example, 1:5) it ground, mixed, mixture is in Ar/H2750 DEG C of carbonization 1h in atmosphere obtain porous carbon-supported defectization vulcanization
Molybdenum elctro-catalyst.
Embodiment 5
The preparation method of the porous carbon-supported defect molybdenum sulfide elctro-catalyst of one kind of the present embodiment, specific preparation step is such as
Under:
(1) preparation of functionalization porous carbon: under magnetic stirring, 0.89g D- xylose and 0.31g phloroglucin are dissolved in
In the mixed solution that 10mL is made of alcohol and water (volume ratio of alcohol to water 1:2).Then, 5mL1mmol/L GO is slowly added into
In solution and by being ultrasonically treated evenly dispersed 0.5h.Then, mixture solution is transferred to 50mL polytetrafluoroethylsubstrate substrate
180 DEG C of heating reaction 16h are warming up in autoclave.Solid product is washed with water and is lyophilized, and obtains porous carbon materials.In nitrogen atmosphere
Under, porous carbon is heated into 2h in 800 DEG C of tube furnaces.Then the porous carbon after carbonization is further added at 90 DEG C with concentrated nitric acid
Hot submersion handles 1h, and products therefrom is functionalization porous carbon.
(2) preparation of porous carbon-supported molybdenum sulfide: 0.2mmol ammonium molybdate and 6mmol thiocarbamide are dissolved in 35mL water, stirred
It mixes uniformly, 0.05g functionalization porous carbon is added in Xiang Shangshu solution, ultrasonic treatment 30min forms uniform suspension.It will suspend
Liquid is transferred in the autoclave of 50mL polytetrafluoroethylsubstrate substrate and is warming up to 200 DEG C of insulation reactions for 24 hours, obtains porous carbon-supported sulphur
Change molybdenum.
(3) preparation of porous carbon-supported defect molybdenum sulfide: by porous carbon-supported material molybdenum sulfide and red phosphorus (mass ratio
Example, 1:10) it ground, mixed, mixture is in Ar/H2750 DEG C of carbonization 1h in atmosphere obtain porous carbon-supported defectization vulcanization
Molybdenum elctro-catalyst.
Gained functionalization porous carbon (a, b) and the middle porous carbon-supported molybdenum sulfide of gained of step (2) in the present embodiment step (1)
Scanning electron microscope (SEM) figure of (c, d) is as shown in Figure 1.The material that can be seen that after freeze-drying from a in Fig. 1 and b is shown
Three-dimensional porous structure contains sheet block structure in part in structure.C and d show MoS in Fig. 12Nanometer sheet is presented petal-shaped and hangs down
It is directly grown in porous carbon substrate, almost without there is agglomeration.Continue to amplify the SEM of the hybrid material, it can be observed that
MoS2The surface of nanometer sheet is relatively smooth, and thickness is about 10-40nm.
The porous carbon-supported molybdenum sulfide of gained and the middle porous carbon-supported defect of gained of step (3) in the present embodiment step (2)
X-ray diffraction (XRD) spectrogram of molybdenum sulfide is as shown in Figure 2.It can be seen that from the XRD spectra of porous carbon-supported molybdenum sulfide
13.77, the peak at 33.38,39.32 and 58.93 ° corresponds to hexagonal crystal system MoS2(002), (100), (103), (110) it is brilliant
Face (JCPDS#73-1508).For the spectrogram of porous carbon-supported defect molybdenum sulfide, 2 θ are 27.77,32.04,42.90,
57.18, the peak at 64.77,67.27,74.04 and 85.44 ° can belong to (001) of MoP phase, (100), (101),
(110), (111), (200), (201) and (112) crystal face (JCPDS#24-0771).
Porous carbon-supported defect molybdenum sulfide (1:10) manufactured in the present embodiment and existing palladium-carbon catalyst (20%Pt/C)
It is as shown in Figure 3 in the polarization curve of 0.5M sulphuric acid electrolyte water hydrogen manufacturing.From figure 3, it can be seen that porous carbon load prepared by the present invention
The water electrolysis hydrogen production of defect molybdenum sulfide is carried in current density 10mA/cm2The overpotential at place is 144mV.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of the molybdenum sulfide elctro-catalyst of porous carbon-supported defect, it is characterised in that including preparing step as follows
It is rapid:
(1) preparation of functionalization porous carbon: under magnetic stirring, monosaccharide and phloroglucin are dissolved in the mixing being made of alcohol and water
In solvent, then addition graphene oxide ultrasonic disperse is uniform, is warming up to 150~200 DEG C of insulation reactions, solid product is through washing
It washs, is freeze-dried, then carries out carbonization treatment at a temperature of inert atmosphere and 700~900 DEG C, products therefrom is heated through concentrated nitric acid
Impregnation obtains functionalization porous carbon；
(2) preparation of porous carbon-supported molybdenum sulfide: ammonium molybdate and thiocarbamide are dissolved in the water, and function obtained by step (1) is then added
Porous carbon can be changed, ultrasonic treatment forms uniform suspension, then heats to 180~240 DEG C of insulation reactions, obtains porous carbon load
Carry molybdenum sulfide；
(3) preparation of porous carbon-supported defect molybdenum sulfide: porous carbon-supported molybdenum sulfide is mixed with red phosphorus, then in hydrogen and
Carbonization treatment at a temperature of the mixed atmosphere of argon gas and 600~900 DEG C, obtains porous carbon-supported defect molybdenum sulfide elctro-catalyst.
2. the preparation method of the molybdenum sulfide elctro-catalyst of the porous carbon-supported defect of one kind according to claim 1, special
Sign is: monosaccharide described in step (1) refers to one of D- xylose, glucose, fructose or two or more mixing.
3. the preparation method of the molybdenum sulfide elctro-catalyst of the porous carbon-supported defect of one kind according to claim 1, special
Sign is: the mass ratio that monosaccharide described in step (1) and phloroglucin are added is (1~3): 1.
4. the preparation method of the molybdenum sulfide elctro-catalyst of the porous carbon-supported defect of one kind according to claim 1, special
Sign is: the in the mixed solvent of the composition of alcohol and water described in step (1), and the volume ratio of alcohol and water is 1:(1~3).
5. the preparation method of the molybdenum sulfide elctro-catalyst of the porous carbon-supported defect of one kind according to claim 1, special
Sign is: the time of insulation reaction described in step (1) is 12~for 24 hours, time of carbonization treatment is 2~5h.
6. the preparation method of the molybdenum sulfide elctro-catalyst of the porous carbon-supported defect of one kind according to claim 1, special
Sign is: the temperature of the processing of concentrated nitric acid hot submersion described in step (1) is 90~120 DEG C, and the time is 1~3h.
7. the preparation method of the molybdenum sulfide elctro-catalyst of the porous carbon-supported defect of one kind according to claim 1, special
Sign is: the ratio between the amount of substance that ammonium molybdate described in step (2) and thiocarbamide are added is (0.1~0.5): (1~10).
8. the preparation method of the molybdenum sulfide elctro-catalyst of the porous carbon-supported defect of one kind according to claim 1, special
Sign is: the time of insulation reaction described in step (2) be 20~for 24 hours.
9. the preparation method of the molybdenum sulfide elctro-catalyst of the porous carbon-supported defect of one kind according to claim 1, special
Sign is: the mass ratio that porous carbon-supported molybdenum sulfide is mixed with red phosphorus described in step (3) is 1:(1~10)；At the carbonization
The time of reason is 1~5h.
10. a kind of molybdenum sulfide elctro-catalyst of porous carbon-supported defect, it is characterised in that: pass through any one of claim 1~9
The method is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811382910.5A CN109482200B (en) | 2018-11-20 | 2018-11-20 | Porous carbon supported defected molybdenum sulfide electrocatalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811382910.5A CN109482200B (en) | 2018-11-20 | 2018-11-20 | Porous carbon supported defected molybdenum sulfide electrocatalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109482200A true CN109482200A (en) | 2019-03-19 |
| CN109482200B CN109482200B (en) | 2021-03-30 |
Family
ID=65697035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811382910.5A Active CN109482200B (en) | 2018-11-20 | 2018-11-20 | Porous carbon supported defected molybdenum sulfide electrocatalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109482200B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111905767A (en) * | 2020-07-29 | 2020-11-10 | 华南农业大学 | Nano pompon-shaped molybdenum sulfide/wood-based carbon porous electrode material and preparation method and application thereof |
| CN114790001A (en) * | 2022-05-06 | 2022-07-26 | 河南农业大学 | Polyacid functionalized nitrogen-rich porous carbon and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101658796A (en) * | 2009-09-17 | 2010-03-03 | 南开大学 | New method for preparing molybdenum phosphide by reducing molybdenum trioxide precursor |
| KR20120098354A (en) * | 2011-02-28 | 2012-09-05 | 고려대학교 산학협력단 | Multicomponent non-pt electrode catalysts and fuel cell including electrode comprising the electrode catalysts |
| CN105126876A (en) * | 2015-09-07 | 2015-12-09 | 复旦大学 | Flowerlike carbon-loaded MoS<2> nano-particle composite and preparation method thereof |
| CN105513832A (en) * | 2015-12-16 | 2016-04-20 | 华南理工大学 | Graphene/porous carbon composite hydrogel, graphene/porous carbon composite aerogel, and preparation methods and applications thereof |
| CN105692580A (en) * | 2014-11-28 | 2016-06-22 | 中国科学院大连化学物理研究所 | Porous carbon material and preparation and application thereof |
| CN107298442A (en) * | 2017-07-15 | 2017-10-27 | 中国海洋大学 | A kind of biomass carbon/molybdenum disulfide nano-composite material and preparation method thereof |
| CN107768663A (en) * | 2017-09-28 | 2018-03-06 | 芜湖恒尼动力电池材料科技有限公司 | The method for preparing the transition metal oxide with oxygen defect |
| CN108217648A (en) * | 2018-01-29 | 2018-06-29 | 山东省圣泉生物质石墨烯研究院 | A kind of compound porous Carbon Materials and preparation method and application |
| CN108452817A (en) * | 2017-02-17 | 2018-08-28 | 中国科学院化学研究所 | A kind of carrier-borne transition metal phosphide and preparation method thereof and its application on catalyzing manufacturing of hydrogen |
| CN108767209A (en) * | 2018-04-26 | 2018-11-06 | 昆明理工大学 | A kind of preparation method of phosphorus/porous carbon/graphene composite material |
-
2018
- 2018-11-20 CN CN201811382910.5A patent/CN109482200B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101658796A (en) * | 2009-09-17 | 2010-03-03 | 南开大学 | New method for preparing molybdenum phosphide by reducing molybdenum trioxide precursor |
| KR20120098354A (en) * | 2011-02-28 | 2012-09-05 | 고려대학교 산학협력단 | Multicomponent non-pt electrode catalysts and fuel cell including electrode comprising the electrode catalysts |
| CN105692580A (en) * | 2014-11-28 | 2016-06-22 | 中国科学院大连化学物理研究所 | Porous carbon material and preparation and application thereof |
| CN105126876A (en) * | 2015-09-07 | 2015-12-09 | 复旦大学 | Flowerlike carbon-loaded MoS<2> nano-particle composite and preparation method thereof |
| CN105513832A (en) * | 2015-12-16 | 2016-04-20 | 华南理工大学 | Graphene/porous carbon composite hydrogel, graphene/porous carbon composite aerogel, and preparation methods and applications thereof |
| CN108452817A (en) * | 2017-02-17 | 2018-08-28 | 中国科学院化学研究所 | A kind of carrier-borne transition metal phosphide and preparation method thereof and its application on catalyzing manufacturing of hydrogen |
| CN107298442A (en) * | 2017-07-15 | 2017-10-27 | 中国海洋大学 | A kind of biomass carbon/molybdenum disulfide nano-composite material and preparation method thereof |
| CN107768663A (en) * | 2017-09-28 | 2018-03-06 | 芜湖恒尼动力电池材料科技有限公司 | The method for preparing the transition metal oxide with oxygen defect |
| CN108217648A (en) * | 2018-01-29 | 2018-06-29 | 山东省圣泉生物质石墨烯研究院 | A kind of compound porous Carbon Materials and preparation method and application |
| CN108767209A (en) * | 2018-04-26 | 2018-11-06 | 昆明理工大学 | A kind of preparation method of phosphorus/porous carbon/graphene composite material |
Non-Patent Citations (2)
| Title |
|---|
| JING-QI CHI ET AL.: ""Heterointerface engineering of trilayer-shelled ultrathin MoS2/MoP/N-doped carbon hollow nanobubbles for efficient hydrogen evolution"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| ZEXING WU ET AL.: ""MoS2–MoP heterostructured nanosheets on polymer-derived carbon as an electrocatalyst for hydrogen evolution reaction"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111905767A (en) * | 2020-07-29 | 2020-11-10 | 华南农业大学 | Nano pompon-shaped molybdenum sulfide/wood-based carbon porous electrode material and preparation method and application thereof |
| CN111905767B (en) * | 2020-07-29 | 2021-11-26 | 华南农业大学 | Nano pompon-shaped molybdenum sulfide/wood-based carbon porous electrode material and preparation method and application thereof |
| CN114790001A (en) * | 2022-05-06 | 2022-07-26 | 河南农业大学 | Polyacid functionalized nitrogen-rich porous carbon and preparation method and application thereof |
| CN114790001B (en) * | 2022-05-06 | 2023-10-03 | 河南农业大学 | Polyacid functionalized nitrogen-rich porous carbon and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109482200B (en) | 2021-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tang et al. | Metal–organic frameworks-derived metal phosphides for electrochemistry application | |
| CN106229521B (en) | A kind of FeCx@NC catalyst with core-casing structure and preparation method thereof | |
| US20240228296A1 (en) | Fabrication method and application of cobalt and nitrogen co-doped three-dimensional structured carbon matrix | |
| CN109778225A (en) | A kind of N, S codope graphene/selenizing molybdenum/CoFe-LDH aeroge and its preparation | |
| CN105174311B (en) | A kind of molybdenum disulfide nano sheet/carbon aerogels hybrid material and preparation method thereof | |
| CN105107536A (en) | Preparation method of polyhedral cobalt phosphide catalyst for hydrogen production through water electrolysis | |
| CN107346826A (en) | A kind of preparation method of the scattered oxygen reduction electro-catalyst of monatomic iron | |
| CN109616671B (en) | Method for preventing intermetallic compound from agglomerating and growing up at high temperature and application | |
| CN106025244A (en) | Nickel selenide/graphene/carbon nanotube composite material and preparation method thereof | |
| CN110152664B (en) | Preparation method and application of one-dimensional cuprous oxide/carbon nano composite catalyst | |
| CN109546162A (en) | A kind of recyclable preparation method of microporous iron-nitrogen-doped carbon catalyst material | |
| CN105797758A (en) | Synthetic method for graphene-loaded MoO2-Mo2C | |
| CN111215056B (en) | Preparation method and application of low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst | |
| CN107321372B (en) | CoS nano particle/N doping RGO liberation of hydrogen composite material preparation method | |
| CN108855145A (en) | A kind of two-step method prepares cobalt sulfide/vulcanization molybdenum composite material and in hydrogen evolution reaction application | |
| CN113862693A (en) | Preparation method and application of nitrogen-doped mesoporous carbon-loaded high-dispersion Ru nanoparticle catalyst | |
| CN108232213A (en) | A kind of nitrogen-doped graphene-carbon nanotube-cobaltosic oxide hybrid material and preparation method thereof | |
| CN113881965B (en) | Metal nanoparticle supported catalyst with biomass carbon source as template and preparation method and application thereof | |
| Ye et al. | Reduced graphene oxide supporting hollow bimetallic phosphide nanoparticle hybrids for electrocatalytic oxygen evolution | |
| CN110474050A (en) | A kind of doping type carbon/manganese sulfide composite material and preparation method thereof | |
| Xie et al. | Metal-organic framework derived Fe3C nanoparticles coupled single-atomic iron for boosting oxygen reduction reaction | |
| Xiao et al. | Three-dimensional cross-linked Co-MoS 2 catalyst on carbon cloth for efficient hydrogen evolution reaction | |
| CN107464938A (en) | A kind of molybdenum carbide/carbon composite with core shell structure and preparation method thereof and the application in lithium-air battery | |
| CN112909271A (en) | Integral transition metal phosphide electrocatalyst with sea urchin-shaped morphology and preparation method and application thereof | |
| CN109482200A (en) | Porous carbon-supported defect molybdenum sulfide elctro-catalyst of one kind and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |